Laundry detergent compositions comprising hydrophobically modified polyamines

ABSTRACT

The present invention relates to hydrophobically modified polyamines and laundry detergent compositions which comprise said polyamines, said compositions comprising:  
     A) from about 0.01%, preferably from about 0.1%, more preferably from about 1%, most preferably from about 3% to about 50%, preferably to about 20%, more preferably to about 10%, most preferably to about 7% by weight, of a hydrophobically modified polyamine having the formula:  
                 
 
      wherein R is C 6 -C 20  linear or branched alkylene, and mixtures thereof; R 1  is an alkyleneoxy unit having the formula:  
     —(R 2 O) x —R 3    
      wherein R 2  is C 2 -C 4  linear or branched alkylene, and mixtures thereof; R 3  is hydrogen, C 1 -C 22  alkyl, C 7 -C 22  alkylenearyl, and mixtures thereof; x is from about 15 to about 30; at least one Q moiety is a hydrophobic quaternizing unit selected from the group consisting of C 8 -C 30  substituted or unsubstituted linear or branched alkyl, C 6 -C 30  substituted or unsubstituted cycloalkyl, C 7 -C 30  substituted or unsubstituted alkylenearyl, and mixtures thereof, and the remaining Q moieties are selected from the group consisting of lone pairs of electrons on the unreacted nitrogens, hydrogen, C 1 -C 30  substituted or unsubstituted linear or branched alkyl, C 3 -C 30  substituted or unsubstituted cycloalkyl, C 7 -C 30  substituted or unsubstituted alkylenearyl, and mixtures thereof; X is an anion present in sufficient amount to provide electronic neutrality; n is from 0 to 3;  
     B) from about 0.01% by weight, of a surfactant system comprising one or more surfactants selected from:  
     i) from 0% to 100% by weight, of one or more anionic surfactants;  
     ii) from 0% to 100% by weight, of one or more nonionic surfactants;  
     iii) optionally from 0.1% to about 80% by weight, of one or more cationic surfactants;  
     iv) optionally from 0.1% to about 80% by weight, of one or more zwitterionic surfactants;  
     v) optionally from 0.1% to about 80% by weight, of one or more ampholytic surfactants; or  
     vi) mixtures thereof;  
     C) the balance carriers and adjunct ingredients.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of U.S. applicationSer. No. 10/129,617 filed on May 8, 2002, which claims the benefit ofU.S. Provisional Application Serial No. 60/164,491 filed on Nov. 9,1999, (now abandoned).

FIELD OF THE INVENTION

[0002] The present invention relates to laundry detergent compositionscomprising one or more hydrophobically modified polyamines which provideenhanced lipid soil removal benefits, inter alia, body soil removal. Thepresent invention further relates to nil surfactant laundry detergentcompositions wherein aqueous solutions of hydrophobically modifiedpolyamines are the foundation for laundry detergent compositions. Thepresent invention also relates to methods for removing body soil fromfabric, inter alia, the collars of wearing apparel.

BACKGROUND OF THE INVENTION

[0003] Fabric, especially clothing, can become soiled with a variety offoreign substances ranging from hydrophobic stains (grease, oil) tohydrophilic stains (clay). The level of cleaning necessary to removeforeign substances depends to a large degree upon the amount of stainwhich is present and to the degree and manner in which the foreignsubstance has contacted the fabric fibers. Grass stains usually involvedirect abrasive contact with vegetative matter thereby producing highlypenetrating stains. Human body oils and perspiration are continuallyproduced and deposited onto fabric while clothing is being worn,especially at the collar, cuffs, and underarm areas. Body oils becomeembedded into the fabric not only by absorption or by wicking of thematerials themselves into the fiber, but also by the mechanical actionof the body against the fabric.

[0004] In many cases a surfactant per se is not all that is necessary toremove unwanted hydrophobic soils and stains. In the case of human bodyoils and other hydrophobic stains on collars, cuffs and other contactareas, perspiration and body oil stains are not fully removed by washingalone. Even hand scrubbing of collars does not ameliorate the dingyappearance of white cotton-comprising fabric. For hydrophobic soils,dispersants are ineffective because they act on soils which are removedand not on those which are embedded throughout the fabric surfacefibers. Formulators have used soil release polymers to attenuate thespreading out and absorption of greasy, oily material onto syntheticfabric, however, cellulosic fiber still presents the laundry formulatorwith the problem of dingy appearance due to human body oils andperspiration stains.

[0005] There is a long felt need in the art for laundry detergentcompositions which can effectively solublize greasy, oily materials fromthe surface fibers of fabric, and once solublized, said oily materialscan then be eliminated by the action of surfactants. There is also along felt need for a cleaning system which effectively removes lipidtype stains which have been worn into fabric by mechanical action ofskin against fabric, for example, at shirt collars and cuffs.

SUMMARY OF THE INVENTION

[0006] It has now been surprisingly discovered that laundry detergentcompositions comprising certain quaternized polyamines have enhancedgreasy soil removal benefits. The polyamines of the present inventionare quaternized alkyleneoxylated, preferably ethyleneoxylated,polyamines having hydrophobic backbone spacers between the backbonenitrogen atoms. Surprisingly, Applicants discovered that the degree ofquaternization and choice of a hydrophobic quaternizing agent can bemanipulated to provide enhanced removal of greasy, oily stains fromclothing either in the presence of detersive surfactants or in theabsence of surfactants. The laundry detergent compositions of thepresent invention are especially effective in removing “ground-in oilystains”, inter alia, perspiration underarm stains, body oils at thecollar and cuffs of shirts. When used together with a suitablesurfactant system, the hydrophobically modified polyamines of thepresent invention provides for removal of stains which were oncebelieved ruinous to fabric, especially cellulose comprising fabric.

[0007] The first aspect of the present invention relates to ahydrophobically modified polyamine having the formula:

[0008] wherein R is C₆-C₁₂ linear or branched alkylene, and mixturesthereof; R¹ is an alkyleneoxy unit having the formula:

—(R²O)_(x)—R³

[0009] wherein R² is C₂-C₄ linear or branched alkylene, and mixturesthereof; R³ is hydrogen, benzyl, and mixtures thereof; x is from about15 to about 30; at least one Q moiety is a hydrophobic quaternizing unitselected from the group consisting of C₈-C₃₀ substituted orunsubstituted linear or branched alkyl, C₆-C₃₀ substituted orunsubstituted cycloalkyl, C₇-C₃₀ substituted or unsubstitutedalkylenearyl, and mixtures thereof, and the remaining Q moieties areselected from the group consisting of lone pairs of electrons on theunreacted nitrogens, hydrogen, C₁-C₃₀ substituted or unsubstitutedlinear or branched alkyl, C₃-C₃₀ substituted or unsubstitutedcycloalkyl, C₇-C₃₀ substituted or unsubstituted alkylenearyl, andmixtures thereof; X is an anion present in sufficient amount to provideelectronic neutrality; n is from 0 to 3.

[0010] The present invention further relates to laundry detergentcompositions comprising:

[0011] A) from about 0.01%, preferably from about 0.1%, more preferablyfrom about 1%, most preferably from about 3% to about 50%, preferably toabout 20%, more preferably to about 10%, most preferably to about 7% byweight, of a hydrophobically modified polyamine having the formula:

[0012]  wherein R is C₆-C₂₀ linear or branched alkylene, and mixturesthereof; R¹ is an alkyleneoxy unit having the formula:

—(R²O)_(x)—R³

[0013]  wherein R² is C₂-C₄ linear or branched alkylene, and mixturesthereof; R³ is hydrogen, C₁-C₂₂ alkyl, C₇-C₂₂ alkylenearyl, and mixturesthereof; x is from about 15 to about 30; at least one Q moiety is ahydrophobic quaternizing unit selected from the group consisting ofC₈-C₃₀ substituted or unsubstituted linear or branched alkyl, C₆-C₃₀substituted or unsubstituted cycloalkyl, C₇-C₃₀ substituted orunsubstituted alkylenearyl, and mixtures thereof, and the remaining Qmoieties are selected from the group consisting of lone pairs ofelectrons on the unreacted nitrogens, hydrogen, C₁-C₃₀ substituted orunsubstituted linear or branched alkyl, C₃-C₃₀ substituted orunsubstituted cycloalkyl, C₇-C₃₀ substituted or unsubstitutedalkylenearyl, and mixtures thereof; X is an anion present in sufficientamount to provide electronic neutrality; n is from 0 to 3;

[0014] B) from about 0.01% by weight, of a surfactant system comprisingone or more surfactants selected from:

[0015] i) from 0% to 100% by weight, of one or more anionic surfactants;

[0016] ii) from 0% to 100% by weight, of one or more nonionicsurfactants;

[0017] iii) optionally from 0.1% to about 80% by weight, of one or morecationic surfactants;

[0018] iv) optionally from 0.1% to about 80% by weight, of one or morezwitterionic surfactants;

[0019] v) optionally from 0.1% to about 80% by weight, of one or moreampholytic surfactants; or

[0020] vi) mixtures thereof;

[0021] C) the balance carriers and adjunct ingredients.

[0022] The present invention further relates to a nil surfactant laundryor cleaning composition comprising:

[0023] a) from about 0.01%, preferably from about 0.1%, more preferablyfrom about 1%, most preferably from about 3% to about 50%, preferably toabout 20%, more preferably to about 10%, most preferably to about 7% byweight, of a hydrophobically modified polyamine having the formula:

[0024]  wherein R is C₆-C₂₀ linear or branched alkylene, and mixturesthereof; R¹ is an alkyleneoxy unit having the formula:

—(R²O)_(x)—R³

[0025]  wherein R² is C₂-C₄ linear or branched alkylene, and mixturesthereof; R³ is hydrogen, C₁-C₂₂ alkyl, C₇-C₂₂ alkylenearyl, and mixturesthereof; x is from about 15 to about 30; at least one Q moiety is ahydrophobic quaternizing unit selected from the group consisting ofC₈-C₃₀ substituted or unsubstituted linear or branched alkyl, C₆-C₃₀substituted or unsubstituted cycloalkyl, C₇-C₃₀ substituted orunsubstituted alkylenearyl, and mixtures thereof, and the remaining Qmoieties are selected from the group consisting of lone pairs ofelectrons on the unreacted nitrogens, hydrogen, C₁-C₃₀ substituted orunsubstituted linear or branched alkyl, C₃-C₃₀ substituted orunsubstituted cycloalkyl, C₇-C₃₀ substituted or unsubstitutedalkylenearyl, and mixtures thereof; X is an anion present in sufficientamount to provide electronic neutrality; n is from 0 to 3; and

[0026] b) the balance carriers and adjunct ingredients.

[0027] The present invention also relates to a method for cleaningfabric, said method comprising the step of contacting an article ofmanufacture comprising fabric, preferably clothing, with an aqueoussolution of a laundry detergent composition comprising a hydrophobicallymodified polyamine of the present invention.

[0028] These and other objects, features and advantages will becomeapparent to those of ordinary skill in the art from a reading of thefollowing detailed description and the appended claims. All percentages,ratios and proportions herein are by weight, unless otherwise specified.All temperatures are in degrees Celsius (° C.) unless otherwisespecified. All documents cited are in relevant part, incorporated hereinby reference.

DETAILED DESCRIPTION OF THE INVENTION

[0029] The present invention relates to hydrophobically modifiedquaternized polyamines which are suitable for use in laundry detergentcompositions. The hydrophobically modified polyamines of the presentinvention provide enhanced body soil and perspiration soil removalbenefits.

[0030] It has been surprisingly discovered that hydrophobically modifiedquaternized polyamines have increased effectiveness when treating fabricwhich is soiled with human body oils, perspiration, etc. Without wishingto be limited by theory, the hydrophobically modified quaternarypolyamines of the present invention have an unexpected balance ofproperties which makes the compounds amenable to penetrating fabric tosolublize greasy, oily stains, while maintaining water solubility, andpreserving the particulate soil suspension properties needed to directthe dirt away from the fabric thereby avoiding re-deposition. In onepreferred embodiment of the present invention, the hydrophobicallymodified polyamines are used to formulate cleaning compositioncomprising nil surfactants. In addition, the hydrophobically modifiedpolyamines of the present invention reinforce the cleaning actions ofhigh suds and high phosphate cleaning systems.

[0031] The hydrophobically modified polyamines of the present inventiondo not aggregate onto the surface of fabric, whereas surfactants have apropensity to aggregate in this manner. Because the polyamines of thepresent invention do not form micelles there is no inter facial tension.This is particularly important with regard to the air/water interfacewhere foam is formed. Therefore, low foaming can be achieved in theabsence of foam reduction adjunct ingredients.

[0032] The polyamines of the present invention, in the absence ofsurfactants, has a surprising effect against surfactant sensitive soilswhich affect fabric, inter alia, dingy soils, grease, and oil.

[0033] When present in laundry detergent compositions, the polyaminesare effective in an amount from about 0.01%, preferably from about 0.1%,more preferably from about 1%, most preferably from about 3% to about50%, preferably to about 20%, more preferably to about 10%, mostpreferably to about 7% by weight, of said laundry detergent composition.

Hydrophobically Modified Quaternized Polyamines

[0034] For the purposes of the present invention the term“hydrophobically modified” is defined herein as the “reaction of alinear polyamine comprising from 2 to 5 nitrogens wherein each nitrogenhas its backbone hydrogens replaced by a polyalkyleneoxy unit comprisingat least about 15 alkyleneoxy units, with at least one nitrogen beingquaternized with a quaternizing agent selected from the group consistingof comprising a linear alkyl moiety having at least 8 carbon atoms, acyclic alkyl moiety having at least 6 carbon atoms, an alkylenearylunit, inter alia, benzyl, having at least 7 carbon atoms, or mixturesthereof”.

[0035] A “polyamine” for the purposes of the present invention is “anamine having less than 6 backbone nitrogen atoms and no branching”,whereas for the purposes of the present invention, amines comprisingmore than 5 nitrogens are defined as “oligomeric amines” (oligoamines)or “polymeric amines” (polyalkyleneamines or polyalkyleneimines).

[0036] The hydrophobically modified polyamines of the present inventionhave the formula:

[0037] wherein R is C₆-C₂₀ linear or branched alkylene, and mixturesthereof; preferably C₆-C₁₂ linear alkylene, more preferably C₆-C₈ linearalkylene, most preferred backbone unit R is hexylene.

[0038] R¹ is an alkyleneoxy unit having the formula:

—(R²O)_(x)—R³

[0039] wherein R is C₂-C₄ linear or branched alkylene, and mixturesthereof. Preferably R² comprises ethylene, 1,2-propylene, and mixturesthereof, preferably each R² unit is an ethylene unit. One embodiment ofthe present invention which provides advantages in a bleach comprisingcomposition relates to hydrophobically modified zwitterionic polyaminescomprising the first 1-6, preferably the first 1-3 of alkyleneoxy unitsas 1,2-propyleneoxy units followed by the balance ethyleneoxy units.

[0040] R³ is hydrogen, C₁-C₂₂ alkyl, C₇-C₂₂ alkylenearyl, and mixturesthereof. R³ is preferably hydrogen, C₁-C₄ alkyl, benzyl, and mixturesthereof; more preferably hydrogen.

[0041] The index x which describes the average number of alkyleneoxyunits attached to the backbone nitrogen is from about 15 to about 30,preferably from 15 to 25, more preferably from 18 to 23, most preferredaverage value of alkyleneoxy units is 20. The formulator will recognizethat when ethoxylating a polyamine, only an average number orstatistical distribution of alkyleneoxy units will be know. Therefore,depending upon how “tightly” or how “exactly” a polyamine isalkoxylated, the average value may vary from embodiment to embodiment.

[0042] At least one Q moiety is a hydrophobic quaternizing unit selectedfrom the group consisting of C₈-C₃₀ substituted or unsubstituted linearor branched alkyl, C₆-C₃₀ substituted or unsubstituted cycloalkyl,C₇-C₃₀ substituted or unsubstituted alkylenearyl, and mixtures thereof;and the remaining Q moieties are selected from the group consisting oflone pairs of electrons on unreacted nitrogens, hydrogen, C₁-C₃₀substituted or unsubstituted linear or branched alkyl, C₃-C₃₀substituted or unsubstituted cycloalkyl, C₇-C₃₀ substituted orunsubstituted alkylenearyl, and mixtures thereof. Preferably at leastone Q moiety is a hydrophobic quaternizing unit selected from the groupconsisting of C₇-C₃₀ substituted or unsubstituted alkylenearyl, andmixtures thereof; more preferably benzyl, substituted benzyl, naphthyl,substituted naphthyl, and mixtures thereof. For the purposes of thepresent invention the formulae:

[0043] stands for the term “naphthyl” depending upon whether said unitcomprises α-substitution or β-substitution. The index w has the valuefrom 0 to 20. Other alkylene aryl units include besides benzyl,alkylenearyl units having the formula:

[0044] wherein the index z is from 1 to 24.

[0045] For the purposes of the present invention the term “substituted”as it applies to alkylenearyl units suitable as Q units, are one or moreC₁-C₁₂ linear or branch alkyl moieties, provided the total number ofcarbon atoms including the aromatic ring does not exceed 30 carbonatoms.

[0046] A non-limiting example of a substitued alkylenearyl unitaccording to the present invention has the formula:

[0047] which is a 3,5-di-tert-butyl benzyl moiety.

[0048] The index n represents the number of secondary nitrogens in thebackbone. The index n has the value from 0 to 3, preferably from 0 to 2,more preferably 1.

[0049] X is an anion present in sufficient amount to provide electronicneutrality. Non-limiting examples of anions are chlorine, bromine,iodine, methylsulfate, and mixtures thereof.

[0050] An example of a preferred hydrophobically modified polyamineaccording to the present invention has the formula:

[0051] wherein X is a water soluble anion selected from the groupconsisting of chlorine, bromine, iodine, methylsulfate, and mixturesthereof.

Surfactant System

[0052] The laundry detergent compositions of the present inventioncomprise from about 0.01%, preferably from about 1%, more preferablyfrom about 5%, most preferably from 10% to about 80%, preferably toabout 50%, more preferably to about 30%, by weight of a surfactantsystem, said surfactant system comprising one or more surfactantsselected from:

[0053] i) from 0%, preferably from about 0.01% to 100%, preferbably to80% by weight, of one or more anionic surfactants;

[0054] ii) from 0%, preferably from about 0.01% to 100%, preferbably to80% by weight, of one or more nonionic surfactants;

[0055] iii) optionally from 0.1% to about 80% by weight, of one or morecationic surfactants;

[0056] iv) optionally from 0.1% to about 80% by weight, of one or morezwitterionic surfactants;

[0057] v) optionally from 0.1% to about 80% by weight, of one or moreampholytic surfactants; or

[0058] vi) mixtures thereof.

[0059] A preferred surfactant system according to the present inventioncomprises from about 0.01% by weight, of one or more surfactantsselected from:

[0060] i) from 1% to about 100% by weight, of an anionic surfactantselected from:

[0061] a) linear alkyl benzene sulfonates;

[0062] b) mid-chain branched aryl sulfonate surfactants having theformula:

[0063]  wherein A is a mid-chain branched alkyl unit having the formula:

[0064]  wherein R and R¹ are each independently hydrogen, C₁-C₃ alkyl,and mixtures thereof, provided the total number of carbon atoms in saidalkyl unit is from 6 to 18 and at least one of R and R¹ is not hydrogen;x is an integer from 0 to 13; y is an integer from 0 to 13; z is 0 or 1;R² is hydrogen, C₁-C₃ alkyl, and mixtures thereof; M′ is a water solublecation with sufficient charge to provide neutrality;

[0065] c) branched alkyl sulfate surfactants having the formula:

CH₃CH₂(CH₂)_(m)CH₂OSO₃M;

[0066]  or the formula:

CH₃CH₂(CH₂)_(m)CH₂(OCH₂CH₂)_(y)OSO₃M;

[0067] d) mid-chain branched alkyl sulfate surfactants having theformula:

[0068]  or the formula:

[0069]  wherein R, R¹, and R² are each independently hydrogen, C₁-C₃alkyl, and mixtures thereof, provided the total number of carbon atomsin said surfactant is from 14 to 20 and at least one of R, R¹, and R² isnot hydrogen; the index w is an integer from 0 to 13; x is an integerfrom 0 to 13; y is an integer from 0 to 13; z is an integer of at least1; provided w+x+y+z is from 8 to 14 and the total number of carbon atomsin a surfactant is from 14 to 20; R³ is ethylene, 1,2-propylene,1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof; theaverage value of the index m is at least about 0.01; M is a watersoluble cation of sufficient charge to provide electronic neutrality;

[0070] ii) from 0% to 100% by weight, of one or more nonionicsurfactants;

[0071] iii) optionally from 0.1% to about 80% by weight, of one or morecationic surfactants;

[0072] iv) optionally from 0.1% to about 80% by weight, of one or morezwitterionic surfactants;

[0073] v) optionally from 0.1% to about 80% by weight, of one or moreampholytic surfactants; or

[0074] vi) mixtures thereof.

[0075] Depending upon the embodiment of the present invention one ormore categories of surfactants may be chosen by the formulator, however,at least one anionic or at least one nonionic surfactant must bepresent. Within each category of surfactant, more than one type ofsurfactant can be selected.

[0076] Nonlimiting examples of surfactants useful herein include:

[0077] a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS);

[0078] b) C₁₀-C₂₀ primary, branched-chain and random alkyl sulfates(AS);

[0079] c) C₁₀-C₁₈ secondary (2,3) alkyl sulfates having the formula:

[0080]  wherein x and (y+1) are integers of at least about 7, preferablyat least about 9; said surfactants disclosed in U.S. Pat. No. 3,234,258Morris, issued Feb. 8, 1966; U.S. Pat. No. 5,075,041 Lutz, issued Dec.24, 1991; U.S. Pat. No. 5,349,101 Lutz et al., issued Sep. 20, 1994; andU.S. Pat. No. 5,389,277 Prieto, issued Feb. 14, 1995 each incorporatedherein by reference;

[0081] d) C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S) wherein preferably xis from 1-7;

[0082] e) C₁₀-C₁₈ alkyl alkoxy carboxylates preferably comprising 1-5ethoxy units;

[0083] f) C₁₂-C₁₈ alkyl ethoxylates, C₆-C₁₂ alkyl phenol alkoxylateswherein the alkoxylate units are a mixture of ethyleneoxy andpropyleneoxy units, C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensateswith ethylene oxide/propylene oxide block polymers inter alia Pluronic®ex BASF which are disclosed in U.S. Pat. No. 3,929,678 Laughlin et al.,issued Dec. 30, 1975, incorporated herein by reference;

[0084] g) Alkylpolysaccharides as disclosed in U.S. Pat. No. 4,565,647Llenado, issued Jan. 26, 1986, incorporated herein by reference;

[0085] h) Polyhydroxy fatty acid amides having the formula:

[0086] wherein R is C₇-C₂₁ linear alkyl, C₇-C₂, branched alkyl, C₇-C₂₁linear alkenyl, C₇-C₂, branched alkenyl, and mixtures thereof.

[0087] R¹ is ethylene; R² is C₃-C₄ linear alkyl, C₃-C₄ branched alkyl,and mixtures thereof; preferably R² is 1,2-propylene. Nonionicsurfactants which comprise a mixture of R¹ and R² units preferablycomprise from about 4 to about 12 ethylene units in combination withfrom about 1 to about 4 1,2-propylene units. The units may bealternating, or grouped together in any combination suitable to theformulator. Preferably the ratio of R¹ units to R² units is from about4:1 to about 8:1. Preferably an R² units (i.e. 1,2-propylene) isattached to the nitrogen atom followed by the balance of the chaincomprising from 4 to 8 ethylene units.

[0088] R³ is hydrogen, C₁-C₄ linear alkyl, C₃-C₄ branched alkyl, andmixtures thereof; preferably hydrogen or methyl, more preferablyhydrogen.

[0089] R⁴ is hydrogen, C₁-C₄ linear alkyl, C₃-C₄ branched alkyl, andmixtures thereof; preferably hydrogen. When the index m is equal to 2the index n must be equal to 0 and the R⁴ unit is absent and is insteadreplaced by a —[(R¹O)_(x)(R²O)_(y)R³] unit.

[0090] The index m is 1 or 2, the index n is 0 or 1, provided that whenm is equal to 1, n is equal to 1; and when m is 2 n is 0; preferably mis equal to 1 and n is equal to one, resulting in one—[(R¹O)_(x)(R²O)_(y)R³] unit and R⁴ being present on the nitrogen. Theindex x is from 0 to about 50, preferably from about 3 to about 25, morepreferably from about 3 to about 10. The index y is from 0 to about 10,preferably 0, however when the index y is not equal to 0, y is from 1 toabout 4. Preferably all of the alkyleneoxy units are ethyleneoxy units.Those skilled in the art of ethoxylated polyoxyalkylene alkyl amidesurface active agents will recognized that the values for the indices xand y are average values and the true values may range over severalvalues depending upon the process used to alkoxylate the amides.

[0091] Suitable means for preparing the polyoxyalkylene alkylamidesurface active agents of the present invention can be found in“Surfactant Science Series”, Editor Martin Schick, Volume I, Chapter 8(1967) and Volume XIX, Chapter 1 (1987) included herein by reference.

[0092] Mid-chain Branched Alkyl Sulfates

[0093] The surfactant systems of the present invention may comprise amid-chain branched alkyl sulfate surfactant and/or a mid-chain branchedalkyl alkoxy sulfate surfactant. Because mid-chain branched alkylsulfate or alkyl alkoxy sulfate surfactants are not required whenmid-chain branched aryl sulfonate surfactants are present, thesurfactant system comprises from 0%, when present from 0.01%, preferablyfrom about 0.1% more preferably from about 1% to about 100%, preferablyto about 80% by weight, preferably to about 60%, most preferably toabout 30% by weight, of the surfactant system. When the mid-chainbranched alkyl sulfate surfactants or mid-chain branched alkyl alkoxysulfate surfactants comprise 100% of the surfactant system saidsurfactants will comprise up to 60% by weight of the final laundrydetergent composition.

[0094] The mid-chain branched alkyl sulfate surfactants of the presentinvention have the formula:

[0095] the alkyl alkoxy sulfates have the formula:

[0096] wherein R, R¹, and R² are each independently hydrogen, C₁-C₃alkyl, and mixtures thereof; provided at least one of R, R¹, and R² isnot hydrogen; preferably R, R¹, and R² are methyl; preferably one of R,R¹, and R² is methyl and the other units are hydrogen. The total numberof carbon atoms in the mid-chain branched alkyl sulfate and alkyl alkoxysulfate surfactants is from 14 to 20; the index w is an integer from 0to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z isan integer of at least 1; provided w+x+y+z is from 8 to 14 and the totalnumber of carbon atoms in a surfactant is from 14 to 20; R³ is C₁-C₄linear or branched alkylene, preferably ethylene, 1,2-propylene,1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof.However, a preferred embodiment of the present invention comprises from1 to 3 units wherein R³ is 1,2-propylene, 1,3-propylene, or mixturesthereof followed by the balance of the R³ units comprising ethyleneunits. Another preferred embodiment comprises R³ units which arerandomly ethylene and 1,2-propylene units. The average value of theindex m is at least about 0.01. When the index m has low values, thesurfactant system comprises mostly alkyl sulfates with a small amount ofalkyl alkoxy sulfate surfactant. Some tertiary carbon atoms may bepresent in the alkyl chain, however, this embodiment is not desired.

[0097] M denotes a cation, preferably hydrogen, a water soluble cation,and mixtures thereof. Non-limiting examples of water soluble cationsinclude sodium, potassium, lithium, ammonium, alkyl ammonium, andmixtures thereof.

[0098] The preferred mid-chain branched alkyl sulfate and alkyl alkoxysulfate surfactants of the present invention are “substantially linear”surfactants. The term “substantially linear” is defined for the purposesof the present invention as “alkyl units which comprise one branchingunit or the chemical reaction products which comprise mixtures of linear(non-branched) alkyl units and alkyl units which comprise one branchingunit”. The term “chemical reaction products” refers to the admixtureobtained by a process wherein substantially linear alkyl units are thedesired product but nevertheless some non-branched alkyl units areformed. When this definition is taken together with preferably one of R,R¹, and R² is methyl and the other units are hydrogen, the preferredmid-chain branched alkyl sulfate and alkyl alkoxy sulfate surfactantscomprise one methyl branch, preferably said methyl branch is not on theα, β, or the second to the last carbon atom. Typically the branchedchains are a mixture of isomers.

[0099] The following illustrate preferred examples of mid-chain branchedalkyl sulfate and alkoxy alkyl sulfate surfactants.

[0100] Mid-chain Branched Aryl Sulphonates

[0101] The surfactant systems of the present invention may comprise amid-chain branched aryl sulphonate surfactant. Because mid-chainbranched aryl sulfonate surfactants are not required when mid-chainbranched alkyl sulfate and/or alkyl alkoxy surfactants are present, thesurfactant system comprises from 0%, when present from 0.01%, preferablyfrom about 0.1% more preferably from about 1% to about 100%, preferablyto about 80% by weight, preferably to about 60%, most preferably toabout 30% by weight, of the surfactant system. When the mid-chainbranched aryl sulphonate surfactants comprise 100% of the surfactantsystem said mid-chain branched aryl sulphonate surfactants will compriseup to 60% by weight of the final laundry detergent composition.

[0102] The mid-chain branched aryl sulphonates of the present inventionhave the formula:

[0103] wherein A is a mid-chain branched alkyl unit having the formula:

[0104] wherein R and R¹ are each independently hydrogen, C₁-C₃ alkyl,and mixtures thereof, provided at least one of R and R¹ is not hydrogen;preferably at least one R or R¹ is methyl; wherein the total number ofcarbon atoms in said alkyl unit is from 6 to 18. Some tertiary carbonatoms may be present in the alkyl chain, however, this embodiment is notdesired.

[0105] The integer x is from 0 to 13. The integer y is from 0 to 13. Theinteger z is either 0 or 1, preferably 0.

[0106] R² is hydrogen, C₁-C₃ alkyl, and mixtures thereof. Preferably R²is hydrogen.

[0107] M′ denotes a water soluble cation with sufficient charge toprovide neutrality, preferably hydrogen, a water soluble cation, andmixtures thereof. Non-limiting examples of water soluble cations includesodium, potassium, lithium, ammonium, alkyl ammonium, and mixturesthereof.

[0108] The preferred mid-chain branched aryl sulphonate surfactants ofthe present invention are “substantially linear aryl” surfactants. Theterm “substantially linear aryl” is defined for the purposes of thepresent invention as “an alkyl unit which is taken together with an arylunit wherein said alkyl unit preferably comprises one branching unit,however, a non-branched linear alkyl unit having an aryl unit bonded tothe 2-carbon position as part of an admixture is included as asubstantially linear aryl surfactant”. The preferred alkyl units do nothave a methyl branch on the second to the last carbon atom. Typicallythe branched chains are a mixture of isomers. However, in the case ofthe mid-chained branched aryl sulphonates of the present invention, therelative position of the aryl moiety is key to the functionality of thesurfactant. Preferably the aryl moiety is attached to the second carbonatom in the branched chain as illustrated herein below.

[0109] The preferred mid-chain branched aryl sulphonates of the presentinvention will comprise a mixture of branched chains. Preferably R¹ ismethyl, the index z is equal to 0, and the sulphate moiety is para (1,4)to the branched alkyl substituent thereby resulting in a “2-phenyl arylsulphonate” defined herein by the general formula:

[0110] Typically 2-phenyl aryl sulphonates are formed as a mixturetogether with “3-phenyl aryl sulphonates” defined herein by the generalformula:

[0111] The surfactant properties of the mid-chain branched arylsulphonates of the present invention can be modified by varying theratio of 2-phenyl to 3-phenyl isomers in the final surfactant mixture. Aconvenient means for describing the relative amounts of isomers presentis the “2/3 phenyl index” defined herein as “100 times the quotient ofthe amount of 2-phenyl isomer present divided by the amount of the3-phenyl isomer which is present”. Any convenient means, NMR, interalia, can be used to determine the relative amounts of isomers present.A preferred 2/3 phenyl index is at least about 275 which corresponds toat least 2.75 times more 2-phenyl isomer present than the 3-phenylisomer in the surfactant mixture. The preferred 2/3-phenyl indexaccording to the present invention is from about 275, more preferablyfrom about 350, most preferably from about 500 to about 10,000,preferably to about 1200, more preferably to about 700.

[0112] Those of ordinary skill in the art will recognize that themid-chain branched surfactants of the present invention will be amixture of isomers and the composition of the mixture will varydepending upon the process which is selected by the formulator to makethe surfactants. For example, the following admixture is considered tocomprise a substantially linear mid-chain branched aryl sulphonateadmixture according to the present invention. Sodiumpara-(7-methylnonan-2-yl)benzenesulphonate, sodiumpara-(6-methylnonan-2-yl)benzenesulphonate, sodiumpara-(7-methylnonan-3-yl)benzene-sulphonate, sodiumpara-(7-methyldecan-2-yl)benzenesulphonate, sodiumpara-(7-methylnonanyl)benzenesulphonate.

Formulations

[0113] The compositions of the present invention may be in any form,inter alia, liquid, granular, paste. Depending upon the specific form ofthe laundry composition, as well as, the expected use thereof, theformulator may will use different surfactant and adjunct ingredientcombinations.

[0114] Preferably the Heavy Duty Granular compositions according to thepresent invention comprise:

[0115] a) from about 0.01%, preferably from about 0.1%, more preferablyfrom 1%, most preferably from 3% to about 20%, preferably to about 10%,more preferably to about 7% by weight, of a hydrophobically modifiedpolyamine; and

[0116] b) from about 0.01% by weight, preferably from about 0.1% morepreferably from about 1% to about 60%, preferably to about 30% byweight, of said composition, of a surfactant system, said surfactantsystem comprising:

[0117] i) from 0.01%, preferably from about 0.1% more preferably fromabout 1% to about 100%, preferably to about 80% by weight, preferably toabout 60%, most preferably to about 30% by weight, of a surfactantselected from the group consisting of alkyl sulfate surfactants, alkoxysulfate surfactants, mid-chain branched alkyl sulfate surfactants,mid-chain branched alkoxy sulfate surfactants, mid-chain branched arylsulfonate surfactants, and mixtures thereof;

[0118] ii) optionally and preferably, from 0.01%, preferably from about0.1% more preferably from about 1% to about 100%, preferably to about80% by weight, preferably to about 60%, most preferably to about 30% byweight, of one or more anionic surfactants;

[0119] iii) optionally, from 0.01%, preferably from about 0.1% morepreferably from about 1% to about 100%, preferably to about 80% byweight, preferably to about 60%, most preferably to about 30% by weight,of one or more nonionic surfactants.

[0120] HDG laundry detergent compositions will typically comprise moreof anionic detersive surfactants. Therefore, the formulator will employa zwitterionic polyamine having a greater number of anionic units thanthe number of backbone cationic units. This net charge balance willameliorate the negative interaction of the surfactant molecules with thehydrophilic soil active zwitterionic polymers.

[0121] By contrast, preferably the Heavy Duty Liquid (HDL) compositionsaccording to the present invention comprise:

[0122] a) from about 0.01%, preferably from about 0.1%, more preferablyfrom 1%, most preferably from 3% to about 20%, preferably to about 10%,more preferably to about 5% by weight, of a zwitterionic polyaminewherein said polyamine comprises less than or equal number of anionicsubstituents than the number of backbone quaternary nitrogen units; and

[0123] b) from about 0.01% by weight, preferably from about 0.1% morepreferably from about 1% to about 60%, preferably to about 30% byweight, of said composition, of a surfactant system, said surfactantsystem comprising:

[0124] i) from 0.01%, preferably from about 0.1% more preferably fromabout 1% to about 100%, preferably to about 80% by weight, preferably toabout 60%, most preferably to about 30% by weight, of a surfactantselected from the group consisting of mid-chain branched alkyl sulfatesurfactants, mid-chain branched alkoxy sulfate surfactants, mid-chainbranched aryl sulfonate surfactants, and mixtures thereof;

[0125] ii) preferably, from 0.01%, preferably from about 0.1% morepreferably from about 1% to about 100%, preferably to about 80% byweight, preferably to about 60%, most preferably to about 30% by weight,of one or more nonionic surfactants, said nonionic surfactants selectedform the group consisting of alcohols, alcohol ethoxylates,polyoxyalkylene alkylamides, and mixtures thereof;

[0126] iii) optionally, from 0.01%, preferably from about 0.1% morepreferably from about 1% to about 100%, preferably to about 80% byweight, preferably to about 60%, most preferably to about 30% by weight,of one or more nonionic surfactants.

[0127] HDL laundry detergent compositions will typically comprise moreof a lesser amount of an anionic detersive surfactant and more nonionicsurfactants. Therefore, the formulator will employ a zwitterionicpolyamine having an equal number of anionic units as the number ofcationic units or a greater number of cationic backbone units than thenumber of anionic units.

[0128] A preferred nil-surfactant Heavy Duty Granular compositionaccording to the present invention comprises:

[0129] a) from about 0.01%, preferably from about 0.1%, more preferablyfrom 1%, most preferably from 3% to about 20%, preferably to about 10%,more preferably to about 7% by weight, of a hydrophobically modifiedpolyamine;

[0130] b) from about 1%, preferably from about 5%, more preferably fromabout 10% to about 80%, preferably to about 50%, more preferably toabout 30% by weight, of detergent builder; and

[0131] c) the balance carriers and adjunct ingredients.

[0132] The nil surfactant formulations of the present invention canfurther comprise a bleaching system as described herein below.Nil-surfactant bleach containing compositions comprise:

[0133] a) from about 0.01%, preferably from about 0.1%, more preferablyfrom 1%, most, preferably from 3% to about 20%, preferably to about 10%,more preferably to about 7% by weight, of a hydrophobically modifiedpolyamine;

[0134] b) from about 1%, preferably from about 5% to about 80%,preferably to about 50% by weight, of the laundry detergent composition,a peroxygen bleaching system comprising:

[0135] i) from about 40%, preferably from about 50%, more preferablyfrom about 60% to about 100%, preferably to about 95%, more preferablyto about 80% by weight, of the bleaching system, a source of hydrogenperoxide;

[0136] ii) optionally from about 0.1%, preferably from about 0.5% toabout 60%, preferably to about 40% by weight, of the beaching system, abeach activator;

[0137] iii) optionally from about 1 ppb (0.0000001%), more preferablyfrom about 100 ppb (0.00001%), yet more preferably from about 500 ppb(0.00005%), still more preferably from about 1 ppm (0.0001%) to about99.9%, more preferably to about 50%, yet more preferably to about 5%,still more preferably to about 500 ppm (0.05%) by weight of thecomposition, of a transition-metal bleach catalyst;

[0138] iv) optionally from about 0.1% by weight, of a pre-formedperoxygen bleaching agent; and

[0139] c) the balance carriers and other adjunct ingredients.

[0140] A preferred nil-surfactant bleaching-contain compositionaccording to the present invention is a composition comprising atransition metal bleach in the absence an added peroxygen bleach. Asdescribed herein above for surfactant containing compositions, sourcesof peroxygen bleaches include, but are not limited to, sources ofhydrogen peroxide inter alia hydrogen peroxide, percarbonate, perborate.Alkali metal and alkaline earth metal percarbonate and perborate aretypically found in laundry bleaching systems. These sources of hydrogenperoxide are typically formulated with one or more bleach activatorsinter alia nonanoyloxybenzenesulfonate (NOBS),tetraacetylethylenediamine (TAED). Bleach activators are typicallyviewed as precursors to the less stable but more reactive peroxyacidbleaching agents. Peroxyacids are formed in situ when the bleachactivator (peroxyacid precursor) reacts with hydrogen peroxide orhydroperoxide anion via a perhydrolysis reaction.

[0141] a) from about 0.01%, preferably from about 0.1%, more preferablyfrom 1%, most preferably from 3% to about 20%, preferably to about 10%,more preferably to about 7% by weight, of a hydrophobically modifiedpolyamine;

[0142] b) from about 1 ppb (0.0000001%), more preferably from about 100ppb (0.00001%), yet more preferably from about 500 ppb (0.00005%), stillmore preferably from about 1 ppm (0.0001%) to about 99.9%, morepreferably to about 50%, yet more preferably to about 5%, still morepreferably to about 500 ppm (0.05%) by weight of the composition, of atransition-metal bleach catalyst; preferably a bleach catalyst selectedfrom the group consisting of5,12-dimethyl-1,5,8,12-tertaaza-bicyclo[6.6.2]-hexadecane,5-ethyl-12-methyl-1,5,8,12-tertaaza-bicyclo[6.6.2]hexadecane,5,12-diethyl-1,5,8,12-tertaaza-bicyclo[6.6.2]hexadecane, and mixturesthereof;

[0143] c) from about 1%, preferably from about 5%, more preferably fromabout 10% to about 80%, preferably to about 50%, more preferably toabout 30% by weight, of detergent builder; and

[0144] d) the balance carriers and other adjunct ingredients

[0145] wherein said composition does not comprise a source of peroxygen.

[0146] A further preferred nil surfactant formulation according to thepresent invention comprises one or more enzymes in combination with thehydrophobically modified polyamines of the present invention. An exampleof an enzyme comprising composition comprises:

[0147] a) from about 0.01%, preferably from about 0.1%, more preferablyfrom 1%, most preferably from 3% to about 20%, preferably to about 10%,more preferably to about 7% by weight, of a hydrophobically modifiedpolyamine;

[0148] b) from 0.0001%, more preferably from 0.0005%, most preferablyfrom 0.001% to 2%, preferably to 0.1%, more preferably to 0.02% byweight, of pure enzyme; and

[0149] c) the balance carriers and other adjunct ingredients.

[0150] An example of a formulation which is suitable as a nil-surfactantlaundry composition comprises:

[0151] a) from about 0.01%, preferably from about 0.1%, more preferablyfrom 1%, most preferably from 3% to about 20%, preferably to about 10%,more preferably to about 7% by weight, of a hydrophobically modifiedpolyamine;

[0152] b) from 0.0001%, more preferably from 0.0005%, most preferablyfrom 0.001% to 2%, preferably to 0.1%, more preferably to 0.02% byweight, of pure enzyme; and

[0153] c) from about 1%, preferably from about 5%, more preferably fromabout 10% to about 80%, preferably to about 50%, more preferably toabout 30% by weight, of detergent builder; and

[0154] d) from about 1%, preferably from about 5% to about 80%,preferably to about 50% by weight, of the laundry detergent composition,a peroxygen bleaching system comprising:

[0155] i) from about 40%, preferably from about 50%, more preferablyfrom about 60% to about 100%, preferably to about 95%, more preferablyto about 80% by weight, of the bleaching system, a source of hydrogenperoxide;

[0156] ii) optionally from about 0.1%, preferably from about 0.5% toabout 60%, preferably to about 40% by weight, of the beaching system, abeach activator;

[0157] iii) optionally from about 1 ppb (0.0000001%), more preferablyfrom about 100 ppb (0.00001%), yet more preferably from about 500 ppb(0.00005%), still more preferably from about 1 ppm (0.0001%) to about99.9%, more preferably to about 50%, yet more preferably to about 5%,still more preferably to about 500 ppm (0.05%) by weight of thecomposition, of a transition-metal bleach catalyst;

[0158] iv) optionally from about 0.1% by weight, of a pre-formedperoxygen bleaching agent; and

[0159] e) the balance carriers and other adjunct ingredients, saidadjunct ingredients are selected from the group consisting of dyetransfer inhibiting agents, scum dispersants, suds suppressors, opticalbrighteners, whitening agents, dye fixing agents, light fadingprotection agents, dispersants, dyes, pigments, colorants, perfumes,germicides, and mixtures thereof.

Bleaching System

[0160] The hydrophobically modified polyamine-comprising laundrydetergent compositions of the present invention may optionally comprisea bleaching system. Bleaching systems typically comprise a “bleachingagent” (source of hydrogen peroxide) and an “initiator” or “catalyst”.

[0161] Preferred laundry detergent compositions of the present inventionwhich comprise a bleaching system, comprise:

[0162] a) from about 0.01% by weight, of a hydrophobically modifiedpolyamine according to the present invention;

[0163] b) from about 0.01% by weight, of a surfactant system comprising:

[0164] i) from 0% to 100% by weight, of the surfactant system one ormore anionic surfactants;

[0165] ii) from 0% to 100% by weight, of the surfactant system one ormore nonionic surfactants;

[0166] iii) optionally from 0.1% to about 80% by weight, of thesurfactant system one or more cationic surfactants;

[0167] iv) optionally from 0.1% to about 80% by weight, of thesurfactant system one or more zwitterionic surfactants;

[0168] v) optionally from 0.1% to about 80% by weight, of the surfactantsystem one or more ampholytic surfactants; or

[0169] vi) mixtures thereof;

[0170] c) from about 1%, preferably from about 5% to about 80%,preferably to about 50% by weight, of the laundry detergent composition,a peroxygen bleaching system comprising:

[0171] i) from about 40%, preferably from about 50%, more preferablyfrom about 60% to about 100%, preferably to about 95%, more preferablyto about 80% by weight, of the bleaching system, a source of hydrogenperoxide;

[0172] ii) optionally from about 0.1%, preferably from about 0.5% toabout 60%, preferably to about 40% by weight, of the beaching system, abeach activator;

[0173] iii) optionally from about 1 ppb (0.0000001%), more preferablyfrom about 100 ppb (0.00001%), yet more preferably from about 500 ppb(0.00005%), still more preferably from about 1 ppm (0.0001%) to about99.9%, more preferably to about 50%, yet more preferably to about 5%,still more preferably to about 500 ppm (0.05%) by weight of thecomposition, of a transition-metal bleach catalyst;

[0174] iv) optionally from about 0.1% by weight, of a pre-formedperoxygen bleaching agent; and

[0175] d) the balance carriers and other adjunct ingredients.

[0176] Bleaching Agents—Hydrogen peroxide sources are described indetail in the herein incorporated Kirk Othmer's Encyclopedia of ChemicalTechnology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300“Bleaching Agents (Survey)”, and include the various forms of sodiumperborate and sodium percarbonate, including various coated and modifiedforms.

[0177] Sources of hydrogen peroxide which are suitable for use in thecompositions of the present invention include, but are not limited to,perborates, percarbonates, perphosphates, persulfates, and mixturesthereof. Preferred sources of hydrogen peroxide are sodium perboratemonohydrate, sodium perborate tetrahydrate, sodium percarbonate andsodium persulfate, more preferably are sodium perborate monohydrate,sodium perborate tetrahydrate, and sodium percarbonate. When present thesource of hydrogen peroxide is present at a level of from about 40%,preferably from about 50%, more preferably from about 60% to about 100%,preferably to about 95%, more preferably to about 80% by weight, of thebleaching system. Embodiments which are bleach comprising pre-soakcompositions may comprise from 5% to 99% of the source of hydrogenperoxide.

[0178] A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with a silicate, borate orwater-soluble surfactants.

[0179] Bleach Activators

[0180] Preferably, the source of hydrogen peroxide (peroxygen bleachcomponent) in the composition is formulated with an activator (peracidprecursor). The activator is present at levels of from about 0.01%,preferably from about 0.5%, more preferably from about 1% to about 15%,preferably to about 10%, more preferably to about 8%, by weight of thecomposition. Also, bleach activators will comprise from about 0.1% toabout 60% by weight, of the beaching system. When the herein describedbleaching system comprises 60% by weight, of an activator (the maximalamount) and said composition (bleaching composition, laundry detergent,or otherwise) comprises 15% by weight of said activator (the maximalamount by weight), said composition will comprise 25% by weight of ableaching system (60% of which is bleach activator, 40% a source ofhydrogen peroxide). However, this is not meant to restrict theformulator to a 60:40 ratio of activator to hydrogen peroxide source.

[0181] Preferably the mole ratio of peroxygen bleaching compound (asAvO) to bleach activator in the present invention generally ranges fromat least 1:1, preferably from about 20:1, more preferably from about10:1 to about 1:1, preferably to about 3:1.

[0182] Preferred activators are selected from the group consisting oftetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL),4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C₁₀-OBS),benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (C₈-OBS),perhydrolyzable esters and mixtures thereof, most preferablybenzoylcaprolactam and benzoylvalerolactam. Particularly preferredbleach activators in the pH range from about 8 to about 9.5 are thoseselected having an OBS or VL leaving group.

[0183] Preferred hydrophobic bleach activators include, but are notlimited to, nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) aminohexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS) an example ofwhich is described in U.S. Pat. No. 5,523,434,dodecanoyloxybenzenesulphonate (LOBS or C₁₂-OBS),10-undecenoyloxybenzenesulfonate (UDOBS or C₁₁-OBS with unsaturation inthe 10 position), and decanoyloxybenzoic acid (DOBA).

[0184] Preferred bleach activators are those described in U.S. Pat. No.5,698,504 Christie et al., issued Dec. 16, 1997; U.S. Pat. No. 5,695,679Christie et al. issued Dec. 9, 1997; U.S. Pat. No. 5,686,401 Willey etal., issued Nov. 11, 1997; U.S. Pat. No. 5,686,014 Hartshorn et al.,issued Nov. 11, 1997; U.S. Pat. No. 5,405,412 Willey et al., issued Apr.11, 1995; U.S. Pat. No. 5,405,413 Willey et al., issued Apr. 11, 1995;U.S. Pat. No. 5,130,045 Mitchel et al., issued Jul. 14, 1992; and U.S.Pat. No. 4,412,934 Chung et al., issued Nov. 1, 1983, and copendingpatent applications U.S. Ser. Nos. 08/709,072, 08/064,564; acyl lactamactivators, as described in U.S. Pat. No. 5,698,504, U.S. Pat. No.5,695,679 and U.S. Pat. No. 5,686,014, each of which is cited hereinabove, are very useful herein, especially the acyl caprolactams (see forexample WO 94-28102 A) and acyl valerolactams, U.S. Pat. No. 5,503,639Willey et al., issued Apr. 2, 1996 all of which are incorporated hereinby reference.

[0185] Quaternary substituted bleach activators may also be included.The present cleaning compositions preferably comprise a quaternarysubstituted bleach activator (QSBA) or a quaternary substituted peracid(QSP); more preferably, the former. Preferred QSBA structures arefurther described in U.S. Pat. No. 5,686,015 Willey et al., issued Nov.11, 1997; U.S. Pat. No. 5,654,421 Taylor et al., issued Aug. 5, 1997;U.S. Pat. No. 5,460,747 Gosselink et al., issued Oct. 24, 1995; U.S.Pat. No. 5,584,888 Miracle et al., issued Dec. 17, 1996; and U.S. Pat.No. 5,578,136 Taylor et al., issued Nov. 26, 1996; all of which areincorporated herein by reference.

[0186] Highly preferred bleach activators useful herein areamide-substituted as described in U.S. Pat. No. 5,698,504, U.S. Pat. No.5,695,679, and U.S. Pat. No. 5,686,014 each of which are cited hereinabove. Preferred examples of such bleach activators include:(6-octanamidocaproyl) oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof.

[0187] Other useful activators, disclosed in U.S. Pat. No. 5,698,504,U.S. Pat. No. 5,695,679, U.S. Pat. No. 5,686,014 each of which is citedherein above and U.S. Pat. No. 4,966,723Hodge et al., issued Oct. 30,1990, include benzoxazin-type activators, such as a C₆H₄ ring to whichis fused in the 1,2-positions a moiety —C(O)OC(R¹)═N—.

[0188] Depending on the activator and precise application, goodbleaching results can be obtained from bleaching systems having within-use pH of from about 6 to about 13, preferably from about 9.0 toabout 10.5. Typically, for example, activators with electron-withdrawingmoieties are used for near-neutral or sub-neutral pH ranges. Alkalis andbuffering agents can be used to secure such pH.

[0189] Transition Metal Bleach Catalyst

[0190] The laundry detergent compositions of the present inventionoptionally comprises a bleaching system which contains one or morebleach catalysts. Selected bleach catalysts inter alia5,12-dimethyl-1,5,8,12-tertaaza-bicyclo[6.6.2]hexadecane manganese (II)chloride may be formulated into bleaching systems which do not require asource of hydrogen peroxide or peroxygen bleach. The compositionscomprise from about 1 ppb (0.0000001%), more preferably from about 100ppb (0.00001%), yet more preferably from about 500 ppb (0.00005%), stillmore preferably from about 1 ppm (0.0001%) to about 99.9%, morepreferably to about 50%, yet more preferably to about 5%, still morepreferably to about 500 ppm (0.05%) by weight of the composition, of atransition-metal bleach catalyst

[0191] Non-limiting examples of suitable manganese-based catalysts aredisclosed in U.S. Pat. No. 5,576,282 Miracle et al., issued Nov. 19,1996; U.S. Pat. No. 5,246,621 Favre et al., issued Sep. 21, 1993; U.S.Pat. No. 5,244,594 Favre et al., issued Sep. 14, 1993; U.S. Pat. No.5,194,416 Jureller et al., issued Mar. 16, 1993; U.S. Pat. No. 5,114,606van Vliet et al., issued May 19, 1992; U.S. Pat. No. 4,430,243 Bragg,issued Feb. 7, 1984; U.S. Pat. No. 5,114,611 van Kralingen, issued May19, 1992; U.S. Pat. No. 4,728,455 Rerek, issued Mar. 1, 1988; U.S. Pat.No. 5,284,944 Madison, issued Feb. 8, 1994; U.S. Pat. No. 5,246,612 vanDijk et al., issued Sep. 21, 1993; U.S. Pat. No. 5,256,779 Kerschner etal., issued Oct. 26, 2993; U.S. Pat. No. 5,280,117 Kerschner et al.,issued Jan. 18, 1994; U.S. Pat. No. 5,274,147 Kerschner et al., issuedDec. 28, 1993; U.S. Pat. No. 5,153,161 Kerschner et al., issued Oct. 6,1992; and U.S. Pat. No. 5,227,084 Martens et al., issued Jul. 13, 1993;and European Pat. App. Pub. Nos. 549,271 A1, 549,272 A1, 544,440 A2, and544,490 A1.

[0192] Non-limiting examples of suitable cobalt-based catalysts aredisclosed in U.S. Pat. No. 5,597,936 Perkins et al., issued Jan. 28,1997; U.S. Pat. No. 5,595,967 Miracle et al., issued Jan. 21, 1997; U.S.Pat. No. 5,703,030 Perkins et al., issued Dec. 30, 1997; U.S. Pat. No.4,810,410 Diakun et al, issued Mar. 7, 1989; M. L. Tobe, “BaseHydrolysis of Transition-Metal Complexes”, Adv. Inorg. Bioinorg. Mech.,(1983), 2, pages 1-94; J. Chem. Ed. (1989), 66 (12), 1043-45; TheSynthesis and Characterization of Inorganic Compounds, W. L. Jolly(Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979);Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979);Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56,22-25 (1952).

[0193] Further examples of preferred macrocyclic ligand comprisingbleach catalysts are described in WO 98/39406 A1 published Sep. 11, 1998and included herein by reference. Suitable examples of these bleachcatalysts include:

[0194] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0195] Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II) hexafluorophosphate

[0196]Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(III) hexafluorophosphate

[0197] Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II) tetrafluoroborate

[0198] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II) hexafluorophosphate

[0199]Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0200] Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II)

[0201]Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecanemanganese(II)

[0202]Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecanemanganese(II)

[0203]Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecanemanganese(II).

[0204] Pre-Formed Bleaching Agents

[0205] The bleaching systems of the present invention may optionallyfurther comprise from 0.1%, preferably from 1%, more preferably from 5%to about 10%, preferably to about 7% by weight, of one or morepre-formed bleaching agents. Pre-formed bleaching materials typicallyhave the general formula:

[0206] wherein R is a C₁-C₂₂ alkylene, C₁-C₂₂ substituted alkylene,phenylene, C₆-C₂₂ substituted phenylene, and mixtures thereof, Y ishydrogen, halogen, alkyl, aryl, —C(O)OH, —C(O)OOH, and mixtures thereof.

[0207] The organic percarboxylic acids usable in the present inventioncan contain either one or two peroxy groups and can be either aliphaticor aromatic. When the organic percarboxylic acid is aliphatic, theunsubstituted acid has the general formula:

[0208] wherein Y can be hydrogen, methyl, methyl chloride, carboxylate,percarboxylate; and n is an integer having the value from 1 to 20.

[0209] When the organic percarboxylic acid is aromatic, theunsubstituted acid has the general formula:

[0210] wherein Y can be hydrogen, alkyl, haloalkyl, carboxylate,percarboxylate, and mixtures thereof.

[0211] Typical monoperoxy percarboxylic acids useful herein includealkyl percarboxylic acids and aryl percarboxylic acids such as:

[0212] i) peroxybenzoic acid and ring-substituted peroxybenzoic acids,e.g., peroxy-o-naphthoic acid;

[0213] ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, e.g. peroxylauric acid, peroxystearic acid, andN,N-phthaloylaminoperoxycaproic acid (PAP).

[0214] Typical diperoxy percarboxylic acids useful herein include alkyldiperoxy acids and aryldiperoxy acids, such as:

[0215] iii) 1,12-diperoxydodecanedioic acid;

[0216] iv) 1,9-diperoxyazelaic acid;

[0217] v) diperoxybrassylic acid; diperoxysebacic acid anddiperoxyisophthalic acid;

[0218] vi) 2-decyldiperoxybutane-1,4-dioic acid;

[0219] vii) 4,4′-sulfonybisperoxybenzoic acid.

[0220] A non-limiting example of a highly preferred pre-formed bleachincludes 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described inU.S. Pat. No. 4,634,551 Burns et al., issued Jan. 6, 1987 includedherein by reference.

[0221] As well as the herein described peroxygen bleaching compositions,the compositions of the present invention may also comprise as thebleaching agent a chlorine-type bleaching material. Such agents are wellknown in the art, and include for example sodium dichloroisocyanurate(“NaDCC”). However, chlorine-type bleaches are less preferred forcompositions which comprise enzymes.

Enzymes

[0222] The term “enzyme” or “detersive enzyme”, as used herein, meansany enzyme having a cleaning, stain removing or otherwise beneficialeffect in a laundry, hard surface cleaning, or other cleaningformulation or composition as described herein. In general, enzymes arepresent in the compositions of the present invention at a level of from0.0001%, more preferably from 0.0005%, most preferably from 0.001% to2%, preferably to 0.1%, more preferably to 0.02% by weight, of pureenzyme. Preferred enzymes are hydrolases such as proteases, amylases andlipases. Preferred enzymes for liquid laundry purposes include, but arenot limited to, inter alia proteases, cellulases, lipases andperoxidases.

[0223] Protease Enzymes

[0224] The preferred liquid laundry detergent compositions according tothe present invention further comprise at least 0.001% by weight, of aprotease enzyme. However, an effective amount of protease enzyme issufficient for use in the liquid laundry detergent compositionsdescribed herein. The term “an effective amount” refers to any amountcapable of producing a cleaning, stain removal, soil removal, whitening,deodorizing, or freshness improving effect on substrates such asfabrics. In practical terms for current commercial preparations, typicalamounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg,of active enzyme per gram of the detergent composition. Statedotherwise, the compositions herein will typically comprise from 0.001%to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.The protease enzymes of the present invention are usually present insuch commercial preparations at levels sufficient to provide from 0.005to 0.1 Anson units (AU) of activity per gram of composition.

[0225] Preferred liquid laundry detergent compositions of the presentinvention comprise modified protease enzymes derived from Bacillusamyloliquefaciens or Bacillus lentus. For the purposes of the presentinvention, protease enzymes derived from B. amyloliquefaciens arefurther referred to as “subtilisin BPN′” also referred to as “ProteaseA” and protease enzymes derived from B. Lentus are further referred toas “subtilisin 309”. For the purposes of the present invention, thenumbering of Bacillus amyloliquefaciens subtilisin, as described in thepatent applications of A. Baeck, et al, entitled “Protease-ContainingCleaning Compositions” having U.S. Ser. No. 08/322,676, serves as theamino acid sequence numbering system for both subtilisin BPN′ andsubtilisin 309.

Derivatives of Bacillus amyloliquefaciens subtilisin-BPN′ enzymes

[0226] A preferred protease enzyme for use in the present invention is avariant of Protease A (BPN′) which is a non-naturally occurring carbonylhydrolase variant having a different proteolytic activity, stability,substrate specificity, pH profile and/or performance characteristic ascompared to the precursor carbonyl hydrolase from which the amino acidsequence of the variant is derived. This variant of BPN′ is disclosed inEP 130,756 A, Jan. 9, 1985.

[0227] Protease B

[0228] A preferred protease enzyme for use in the present invention isProtease B. Protease B is a non-naturally occurring carbonyl hydrolasevariant having a different proteolytic activity, stability, substratespecificity, pH profile and/or performance characteristic as compared tothe precursor carbonyl hydrolase from which the amino acid sequence ofthe variant is derived. Protease B is a variant of BPN′ in whichtyrosine is replaced with leucine at position +217 and as furtherdisclosed in EP 303,761 A, Apr. 28, 1987 and EP 130,756 A, Jan. 9, 1985.

[0229] Protease C

[0230] A preferred protease enzyme for use in the compositions of thepresent invention Protease C. Protease C is a variant of an alkalineserine protease from Bacillus in which lysine replaced arginine atposition 27, tyrosine replaced valine at position 104, serine replacedasparagine at position 123, and alanine replaced threonine at position274. Protease C is described in EP 90915958:4, corresponding to WO91/06637, Published May 16, 1991. Genetically modified variants,particularly of Protease C, are also included herein.

[0231] Protease D

[0232] A preferred protease enzyme for use in the present invention isProtease D. Protease D is a carbonyl hydrolase variant derived fromBacillus lentus subtilisin as described in WO 95/10615 published Apr.20, 1995 by Genencor International.

[0233] A further preferred protease enzyme for use in combination withthe modified polyamines of the present invention is ALCALASE® from Novo.Another suitable protease is obtained from a strain of Bacillus, havingmaximum activity throughout the pH range of 8-12, developed and sold asESPERASE® by Novo Industries A/S of Denmark, hereinafter “Novo”. Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include SAVINASE® from Novoand MAXATASE® from International Bio-Synthetics, Inc., The Netherlands.See also a high pH protease from Bacillus sp. NCIMB 40338 described inWO 9318140 A to Novo. Enzymatic detergents comprising protease, one ormore other enzymes, and a reversible protease inhibitor are described inWO 9203529 A to Novo. Other preferred proteases include those of WO9510591 A to Procter & Gamble. When desired, a protease having decreasedadsorption and increased hydrolysis is available as described in WO9507791 to Procter & Gamble. A recombinant trypsin-like protease fordetergents suitable herein is described in WO 9425583 to Novo.

[0234] Other particularly useful proteases are described in PCTApplication Nos. PCT/US98/22588, PCT/US98/22482 and PCT/US98/22486 allfiled on Oct. 23, 1998 from The Procter & Gamble Company.

[0235] Also suitable for the present invention are proteases describedin patent applications EP 251 446 and WO 91/06637, protease BLAP®described in WO91/02792 and their variants described in WO 95/23221.

[0236] See also a high pH protease from Bacillus sp. NCIMB 40338described in WO 93/18140 A to Novo. Enzymatic detergents comprisingprotease, one or more other enzymes, and a reversible protease inhibitorare described in WO 92/03529 A to Novo. When desired, a protease havingdecreased adsorption and increased hydrolysis is available as describedin WO 95/07791 to Procter & Gamble. A recombinant trypsin-like proteasefor detergents suitable herein is described in WO 94/25583 to Novo.Other suitable proteases are described in EP 516 200 by Unilever.

[0237] Commercially available proteases useful in the present inventionare known as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® andKANNASE® all from Novo Nordisk A/S of Denmark, and as MAXATASE®,MAXACAL®, PROPERASE® and MAXAPEM® all from Genencor International(formerly Gist-Brocades of The Netherlands). A preferred protease foruse in the present invention is the protease enzyme as described inWO99/20771 published Apr. 29, 1999.

[0238] In addition to the above-described protease enzymes, otherenzymes suitable for use in the liquid laundry detergent compositions ofthe present invention are further described herein below.

[0239] Other Enzymes

[0240] Enzymes in addition to the protease enzyme can be included in thepresent detergent compositions for a variety of purposes, includingremoval of protein-based, carbohydrate-based, or triglyceride-basedstains from surfaces such as textiles, for the prevention of refugee dyetransfer, for example in laundering, and for fabric restoration.Suitable enzymes include amylases, lipases, cellulases, peroxidases, andmixtures thereof of any suitable origin, such as vegetable, animal,bacterial, fungal and yeast origin. Preferred selections are influencedby factors such as pH-activity and/or stability optima, thermostability,and stability to active detergents, builders and the like. In thisrespect bacterial or fungal enzymes are preferred, such as bacterialamylases and proteases, and fungal cellulases.

[0241] Amylases suitable herein include, for example, α-amylasesdescribed in GB 1,296,839 to Novo; RAPIDASE®, InternationalBio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo isespecially useful. Engineering of enzymes for improved stability, e.g.,oxidative stability, is known. See, for example J. Biological Chem.,Vol. 260, No. 11, June 1985, pp 6518-6521 and WO 9402597 to Novo, Feb.3, 1994, and WO 9509909 A to Novo.

[0242] Cellulases usable herein include both bacterial and fungal types,preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307, Barbesgoard et al, Mar. 6, 1984, discloses suitable fungalcellulases from Humicola insolens or Humicola strain DSM1800 or acellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk,Dolabella Auricula Solander. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® (Novo) isespecially useful. See also WO 9117243 to Novo.

[0243] Suitable lipase enzymes for detergent usage include thoseproduced by microorganisms of the Pseudomonas group, such as Pseudomonasstutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases inJapanese Patent Application 53,20487, laid open Feb. 24, 1978. Thislipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,under the trade name Lipase P “Amano,” or “Amano-P.” Other suitablecommercial lipases include Amano-CES, lipases ex Chromobacter viscosum,e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo JozoCo., Tagata, Japan; Chromobacter viscosum lipases from U.S. BiochemicalCorp., U.S.A. and Disoynth Co., The Netherlands, and lipases exPseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosaand commercially available from Novo, see also EP 341,947, is apreferred lipase for use herein. Lipase and amylase variants stabilizedagainst peroxidase enzymes are described in WO 9414951 A to Novo. Seealso WO 9205249 and RD 94359044.

[0244] Cutinase enzymes suitable for use herein are described in WO8809367 A to Genencor.

[0245] Peroxidase enzymes may be used in combination with oxygensources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for“solution bleaching” or prevention of transfer of dyes or pigmentsremoved from substrates during the wash to other substrates present inthe wash solution. Known peroxidases include horseradish peroxidase,ligninase, and haloperoxidases such as chloro- or bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed in WO89099813 A, Oct. 19, 1989 to Novo and WO 8909813 A to Novo.

[0246] A range of enzyme materials and means for their incorporationinto synthetic detergent compositions is also disclosed in WO 9307263 Aand WO 9307260 A to Genencor International, WO 8908694 A to Novo, andU.S. Pat. No. 3,553,139 McCarty et al., issued Jan. 5, 1971. Enzymes arefurther disclosed in U.S. Pat. No. 4,101,457 Place et al, issued Jul.18, 1978, and U.S. Pat. No. 4,507,219 Hughes, issued Mar. 26, 1985.Enzyme materials useful for liquid detergent formulations, and theirincorporation into such formulations, are disclosed in U.S. Pat. No.4,261,868 Hora et al., issued Apr. 14, 1981. Enzymes for use herein canbe stabilized by various techniques. Enzyme stabilization techniques aredisclosed and exemplified in U.S. Pat. No. 3,600,319 Gedge et al.,issued Aug. 17, 1971; EP 199,405 and EP 200,586, Oct. 29, 1986, Venegas.Enzyme stabilization systems are also described, for example, in U.S.Pat. No. 3,519,570. A useful Bacillus, sp. AC13 giving proteases,xylanases and cellulases, is described in WO 9401532 A to Novo.

[0247] Enzyme Stabilizing System

[0248] Enzyme-containing, including but not limited to, liquidcompositions, herein may comprise from about 0.001%, preferably fromabout 0.005%, more preferably from about 0.01% to about 10%, preferablyto about 8%, more preferably to about 6% by weight, of an enzymestabilizing system. The enzyme stabilizing system can be any stabilizingsystem which is compatible with the detersive enzyme. Such a system maybe inherently provided by other formulation actives, or be addedseparately, e.g., by the formulator or by a manufacturer ofdetergent-ready enzymes. Such stabilizing systems can, for example,comprise calcium ion, boric acid, propylene glycol, short chaincarboxylic acids, boronic acids, and mixtures thereof, and are designedto address different stabilization problems depending on the type andphysical form of the detergent composition.

[0249] One stabilizing approach is the use of water-soluble sources ofcalcium and/or magnesium ions in the finished compositions which providesuch ions to the enzymes. Calcium ions are generally more effective thanmagnesium ions and are preferred herein if only one type of cation isbeing used. Typical detergent compositions, especially liquids, willcomprise from about 1 to about 30, preferably from about 2 to about 20,more preferably from about 8 to about 12 millimoles of calcium ion perliter of finished detergent composition, though variation is possibledepending on factors including the multiplicity, type and levels ofenzymes incorporated. Preferably water-soluble calcium or magnesiumsalts are employed, including for example calcium chloride, calciumhydroxide, calcium formate, calcium malate, calcium maleate, calciumhydroxide and calcium acetate; more generally, calcium sulfate ormagnesium salts corresponding to the exemplified calcium salts may beused. Further increased levels of Calcium and/or Magnesium may of coursebe useful, for example for promoting the grease-cutting action ofcertain types of surfactant.

[0250] Another stabilizing approach is by use of borate speciesdisclosed in U.S. Pat. No. 4,537,706 Severson, issued Aug. 27, 1985.Borate stabilizers, when used, may be at levels of up to 10% or more ofthe composition though more typically, levels of up to about 3% byweight of boric acid or other borate compounds such as borax ororthoborate are suitable for liquid detergent use. Substituted boricacids such as phenylboronic acid, butaneboronic acid,p-bromophenylboronic acid or the like can be used in place of boric acidand reduced levels of total boron in detergent compositions may bepossible though the use of such substituted boron derivatives.

[0251] Stabilizing systems of certain cleaning compositions may furthercomprise from 0, preferably from about 0.01% to about 10%, preferably toabout 6% by weight, of chlorine bleach scavengers, added to preventchlorine bleach species present in many water supplies from attackingand inactivating the enzymes, especially under alkaline conditions.While chlorine levels in water may be small, typically in the range fromabout 0.5 ppm to about 1.75 ppm, the available chlorine in the totalvolume of water that comes in contact with the enzyme, for exampleduring fabric-washing, can be relatively large; accordingly, enzymestability to chlorine in-use is sometimes problematic. Since perborateor percarbonate, which have the ability to react with chlorine bleach,may present in certain of the instant compositions in amounts accountedfor separately from the stabilizing system, the use of additionalstabilizers against chlorine, may, most generally, not be essential,though improved results may be obtainable from their use. Suitablechlorine scavenger anions are widely known and readily available, and,if used, can be salts containing ammonium cations with sulfite,bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such ascarbamate, ascorbate, etc., organic amines such asethylenediaminetetraacetic acid (EDTA) or alkali metal salt thereof,monoethanolamine (MEA), and mixtures thereof can likewise be used.Likewise, special enzyme inhibition systems can be incorporated suchthat different enzymes have maximum compatibility. Other conventionalscavengers such as bisulfate, nitrate, chloride, sources of hydrogenperoxide such as sodium perborate tetrahydrate, sodium perboratemonohydrate and sodium percarbonate, as well as phosphate, condensedphosphate, acetate, benzoate, citrate, formate, lactate, malate,tartrate, salicylate, etc., and mixtures thereof can be used if desired.In general, since the chlorine scavenger function can be performed byingredients separately listed under better recognized functions, (e.g.,hydrogen peroxide sources), there is no absolute requirement to add aseparate chlorine scavenger unless a compound performing that functionto the desired extent is absent from an enzyme-containing embodiment ofthe invention; even then, the scavenger is added only for optimumresults. Moreover, the formulator will exercise a chemist's normal skillin avoiding the use of any enzyme scavenger or stabilizer which ismajorly incompatible, as formulated, with other reactive ingredients, ifused. In relation to the use of ammonium salts, such salts can be simplyadmixed with the detergent composition but are prone to adsorb waterand/or liberate ammonia during storage. Accordingly, such materials, ifpresent, are desirably protected in a particle such as that described inU.S. Pat. No. 4,652,392 Baginski et al., issued Mar. 24, 1987.

Adjunct Ingredients

[0252] The following are non-limiting examples of adjunct ingredientsuseful in the laundry compositions of the present invention, saidadjunct ingredients include builders, optical brighteners, soil releasepolymers, dye transfer agents, dispersents, enzymes, suds suppressers,dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators,fluorescers, fabric conditioners, hydrolyzable surfactants,preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkageagents, anti-wrinkle agents, germicides, fungicides, anti corrosionagents, and mixtures thereof.

[0253] Builders—The laundry detergent compositions of the presentinvention preferably comprise one or more detergent builders or buildersystems. When present, the compositions will typically comprise at leastabout 1% builder, preferably from about 5%, more preferably from about10% to about 80%, preferably to about 50%, more preferably to about 30%by weight, of detergent builder.

[0254] The level of builder can vary widely depending upon the end useof the composition and its desired physical form. When present, thecompositions will typically comprise at least about 1% builder.Formulations typically comprise from about 5% to about 50%, moretypically about 5% to about 30%, by weight, of detergent builder.Granular formulations typically comprise from about 10% to about 80%,more typically from about 15% to about 50% by weight, of the detergentbuilder. Lower or higher levels of builder, however, are not meant to beexcluded.

[0255] Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate builders arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called “weak” builders(as compared with phosphates) such as citrate, or in the so-called“underbuilt” situation that may occur with zeolite or layered silicatebuilders.

[0256] Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂:Na₂O ratio in the range 1.6:1 to 3.2:1and layered silicates, such as the layered sodium silicates described inU.S. Pat. No. 4,664,839 Rieck, issued May 12, 1987. NaSKS-6 is thetrademark for a crystalline layered silicate marketed by Hoechst(commonly abbreviated herein as “SKS-6”). Unlike zeolite builders, theNa SKS-6 silicate builder does not contain aluminum. NaSKS-6 has thedelta-Na₂SiO₅ morphology form of layered silicate. It can be prepared bymethods such as those described in German DE-A-3,417,649 andDE-A-3,742,043. SKS-6 is a highly preferred layered silicate for useherein, but other such layered silicates, such as those having thegeneral formula NaMSi_(x)O_(2x+1).yH₂O wherein M is sodium or hydrogen,x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to20, preferably 0 can be used herein. Various other layered silicatesfrom Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, betaand gamma forms. As noted above, the delta-Na₂SiO₅ (NaSKS-6 form) ismost preferred for use herein. Other silicates may also be useful suchas for example magnesium silicate, which can serve as a crispening agentin granular formulations, as a stabilizing agent for oxygen bleaches,and as a component of suds control systems.

[0257] Examples of carbonate builders are the alkaline earth and alkalimetal carbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

[0258] Aluminosilicate builders are useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

[M_(z)(zAlO₂)_(y)].xH₂O

[0259] wherein z and y are integers of at least 6, the molar ratio of zto y is in the range from 1.0 to about 0.5, and x is an integer fromabout 15 to about 264.

[0260] Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂O

[0261] wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0-10) may also beused herein. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter.

[0262] Organic detergent builders suitable for the purposes of thepresent invention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, “poly-carboxylate” refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

[0263] Included among the polycarboxylate builders are a variety ofcategories of useful materials. One important category ofpolycarboxylate builders encompasses the ether polycarboxylates,including oxydisuccinate, as disclosed in U.S. Pat. No. 3,128,287 Berg,issued Apr. 7, 1964, and U.S. Pat. No. 3,635,830 Lamberti et al., issuedJan. 18, 1972. See also “TMS/TDS” builders of U.S. Pat. No. 4,663,071Bush et al., issued May 5, 1987. Suitable ether polycarboxylates alsoinclude cyclic compounds, particularly alicyclic compounds, such asthose described in U.S. Pat. No. 3,923,679 Rapko, issued Dec. 2, 1975;U.S. Pat. No. 4,158,635 Crutchfield et al., issued Jun. 19, 1979; U.S.Pat. No. 4,120,874 Crutchfield et al., issued Oct. 17, 1978; and U.S.Pat. No. 4,102,903 Crutchfield et al., issued Jul. 25, 1978.

[0264] Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid,and carboxymethyloxysuccinic acid, the various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxy-disuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

[0265] Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

[0266] Also suitable in the detergent compositions of the presentinvention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the relatedcompounds disclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28,1986. Useful succinic acid builders include the C₅-C₂₀ alkyl and alkenylsuccinic acids and salts thereof. A particularly preferred compound ofthis type is dodecenylsuccinic acid. Specific examples of succinatebuilders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

[0267] Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al., issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

[0268] Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

[0269] In situations where phosphorus-based builders can be used, andespecially in the formulation of bars used for hand-launderingoperations, the various alkali metal phosphates such as the well-knownsodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see,for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148and 3,422,137) can also be used.

[0270] Dispersants

[0271] A description of other suitable polyalkyleneimine dispersantswhich may be optionally combined with the bleach stable dispersants ofthe present invention can be found in U.S. Pat. No. 4,597,898 VanderMeer, issued Jul. 1, 1986; European Patent Application 111,965 Oh andGosselink, published Jun. 27, 1984; European Patent Application 111,984Gosselink, published Jun. 27, 1984; European Patent Application 112,592Gosselink, published Jul. 4, 1984; U.S. Pat. No. 4,548,744 Connor,issued Oct. 22, 1985; and U.S. Pat. No. 5,565,145 Watson et al., issuedOct. 15, 1996; all of which are included herein by reference. However,any suitable clay/soil dispersant or anti-redepostion agent can be usedin the laundry compositions of the present invention.

[0272] In addition, polymeric dispersing agents which include polymericpolycarboxylates and polyethylene glycols, are suitable for use in thepresent invention. Polymeric polycarboxylate materials can be preparedby polymerizing or copolymerizing suitable unsaturated monomers,preferably in their acid form. Unsaturated monomeric acids that can bepolymerized to form suitable polymeric polycarboxylates include acrylicacid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid,aconitic acid, mesaconic acid, citraconic acid and methylenemalonicacid. The presence in the polymeric polycarboxylates herein or monomericsegments, containing no carboxylate radicals such as vinylmethyl ether,styrene, ethylene, etc. is suitable provided that such segments do notconstitute more than about 40% by weight.

[0273] Particularly suitable polymeric polycarboxylates can be derivedfrom acrylic acid. Such acrylic acid-based polymers which are usefulherein are the water-soluble salts of polymerized acrylic acid. Theaverage molecular weight of such polymers in the acid form preferablyranges from about 2,000 to 10,000, more preferably from about 4,000 to7,000 and most preferably from about 4,000 to 5,000. Water-soluble saltsof such acrylic acid polymers can include, for example, the alkalimetal, ammonium and substituted ammonium salts. Soluble polymers of thistype are known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in U.S. Pat. No. 3,308,067Diehl, issued Mar. 7, 1967.

[0274] Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000, preferably from about 5,000, morepreferably from about 7,000 to 100,000, more preferably to 75,000, mostpreferably to 65,000. The ratio of acrylate to maleate segments in suchcopolymers will generally range from about 30:1 to about 1:1, morepreferably from about 10:1 to 2:1. Water-soluble salts of such acrylicacid/maleic acid copolymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble acrylate/maleatecopolymers of this type are known materials which are described inEuropean Patent Application No. 66915, published Dec. 15, 1982, as wellas in EP 193,360, published Sep. 3, 1986, which also describes suchpolymers comprising hydroxypropylacrylate. Still other useful dispersingagents include the maleic/acrylic/vinyl alcohol terpolymers. Suchmaterials are also disclosed in EP 193,360, including, for example, the45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

[0275] Another polymeric material which can be included is polyethyleneglycol (PEG). PEG can exhibit dispersing agent performance as well asact as a clay soil removal-antiredeposition agent. Typical molecularweight ranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

[0276] Polyaspartate and polyglutamate dispersing agents may also beused, especially in conjunction with zeolite builders. Dispersing agentssuch as polyaspartate preferably have a molecular weight (avg.) of about10,000.

[0277] Soil Release Agents

[0278] The compositions according to the present invention mayoptionally comprise one or more soil release agents. If utilized, soilrelease agents will generally comprise from about 0.01%, preferably fromabout 0.1%, more preferably from about 0.2% to about 10%, preferably toabout 5%, more preferably to about 3% by weight, of the composition.Polymeric soil release agents are characterized by having bothhydrophilic segments, to hydrophilize the surface of hydrophobic fibers,such as polyester and nylon, and hydrophobic segments, to deposit uponhydrophobic fibers and remain adhered thereto through completion of thelaundry cycle and, thus, serve as an anchor for the hydrophilicsegments. This can enable stains occuring subsequent to treatment withthe soil release agent to be more easily cleaned in later washingprocedures.

[0279] The following, all included herein by reference, describe soilrelease polymers suitable for use in the present invention. U.S. Pat.No. 5,843,878 Gosselink et al., issued Dec. 1, 1998; U.S. Pat. No.5,834,412 Rohrbaugh et al., issued Nov. 10, 1998; U.S. Pat. No.5,728,671 Rohrbaugh et al., issued Mar. 17, 1998; U.S. Pat. No.5,691,298 Gosselink et al., issued Nov. 25, 1997; U.S. Pat. No.5,599,782 Pan et al., issued Feb. 4, 1997; U.S. Pat. No. 5,415,807Gosselink et al., issued May 16, 1995; U.S. Pat. No. 5,182,043 Morrallet al., issued Jan. 26, 1993; U.S. Pat. No. 4,956,447 Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 4,976,879 Maldonado et al. issuedDec. 11, 1990; U.S. Pat. No. 4,968,451 Scheibel et al., issued Nov. 6,1990; U.S. Pat. No. 4,925,577 Borcher, Sr. et al., issued May 15, 1990;U.S. Pat. No. 4,861,512 Gosselink, issued Aug. 29, 1989; U.S. Pat. No.4,877,896 Maldonado et al., issued Oct. 31, 1989; U.S. Pat. No.4,771,730 Gosselink et al., issued Oct. 27, 1987; U.S. Pat. No. 711,730Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580 Gosselinkissued Jan. 26, 1988; U.S. Pat. No. 4,000,093 Nicol et al., issued Dec.28, 1976; U.S. Pat. No. 3,959,230 Hayes, issued May 25, 1976; U.S. Pat.No. 3,893,929 Basadur, issued Jul. 8, 1975; and European PatentApplication 0 219 048, published Apr. 22, 1987 by Kud et al.

[0280] Further suitable soil release agents are described in U.S. Pat.No. 4,201,824 Voilland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.;U.S. Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681 Ruppert etal.; U.S. Pat. No. 4,220,918; U.S. Pat. No. 4,787,989; EP 279,134 A,1988 to Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE2,335,044 to Unilever N. V., 1974; all incorporated herein by reference.

Method of Use

[0281] The present invention further relates to a method for removinghydrophobic soils, inter alia, body oils, perspiration and other humanbody soils form fabric, preferably clothing, said method comprising thestep of contacting fabric in need of cleaning with an aqueous solutioncontaining at least 0.01% by weight, of a laundry detergent compositioncomprising:

[0282] A) from about 0.01% by weight of a hydrophobically modifiedpolyamine having the formula:

[0283]  wherein R is C₅-C₂₀ linear or branched alkylene, and mixturesthereof; R¹ is an alkyleneoxy unit having the formula:

—(R²O)_(x)—R³

[0284]  wherein R² is C₂-C₄ linear or branched alkylene, and mixturesthereof; R³ is hydrogen, C₁-C₂₂ alkyl, C₇-C₂₂ alkylenearyl, an anionicunit, and mixtures thereof; x is from about 15 to about 30; at least oneQ moiety is a hydrophobic quaternizing unit selected from the groupconsisting of C₈-C₃₀ substituted or unsubstituted linear or branchedalkyl, C₆-C₃₀ substituted or unsubstituted cycloalkyl, C₇-C₃₀substituted or unsubstituted alkylenearyl, and mixtures thereof, and theremaining Q moieties are selected from the group consisting of lonepairs of electrons on the unreacted nitrogens, hydrogen, C₁-C₃₀substituted or unsubstituted linear or branched alkyl, C₃-C₃₀substituted or unsubstituted cycloalkyl, C₇-C₃₀ substituted orunsubstituted alkylenearyl, and mixtures thereof; X is an anion presentin sufficient amount to provide electronic neutrality; n is from 0 to 4;

[0285] B) from about 0.01% by weight, of a surfactant system comprisingone or more surfactants selected from:

[0286] i) from 0% to 100% by weight, of one or more anionic surfactants;

[0287] ii) from 0% to 100% by weight, of one or more nonionicsurfactants;

[0288] iii) optionally from 0.1% to about 80% by weight, of one or morecationic surfactants;

[0289] iv) optionally from 0.1% to about 80% by weight, of one or morezwitterionic surfactants;

[0290] v) optionally from 0.1% to about 80% by weight, of one or moreampholytic surfactants; or

[0291] vi) mixtures thereof;

[0292] C) the balance carriers and adjunct ingredients

[0293] Preferably the aqueous solution comprises at least about 0.01%(100 ppm), preferably at least about 1% (1000 ppm) by weight, of saidlaundry detergent composition.

[0294] The compositions of the present invention can be suitablyprepared by any process chosen by the formulator, non-limiting examplesof which are described in U.S. Pat. No. 5,691,297 Nassano et al., issuedNov. 11, 1997; U.S. Pat. No. 5,574,005 Welch et al., issued Nov. 12,1996; U.S. Pat. No. 5,569,645 Dinniwell et al., issued Oct. 29, 1996;U.S. Pat. No. 5,565,422 Del Greco et al., issued Oct. 15, 1996; U.S.Pat. No. 5,516,448 Capeci et al., issued May 14, 1996; U.S. Pat. No.5,489,392 Capeci et al., issued Feb. 6, 1996; U.S. Pat. No. 5,486,303Capeci et al., issued Jan. 23, 1996 all of which are incorporated hereinby reference.

EXAMPLE 1 Synthesis of Ethoxylated (E20) Bis(hexamethylene)triamineTribenzyl Quaternary Ammonium Bromide

[0295] Ethoxylation of Bis(hexamethylene)triamine to Average E20 perNH—The ethoxylation is conducted in a 2 gallon stirred stainless steelautoclave equipped for temperature measurement and control, pressuremeasurement, vacuum and inert gas purging, sampling, and forintroduction of ethylene oxide as a liquid. A ˜20 lb. net cylinder ofethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid bya pump to the autoclave with the cylinder placed on a scale so that theweight change of the cylinder could be monitored.

[0296] A 362 g portion of Bis(hexamethylene)triamine (BHMT) (m.w. 215,(Aldrich), 1.68 moles, 5.04 moles nitrogen, 8.4 moles ethoxylatable (NH)sites, is added to the autoclave. The autoclave is then sealed andpurged of air (by applying vacuum to minus 28″ Hg followed bypressurization with nitrogen to 250 psia, then venting to atmosphericpressure). The autoclave contents are heated to 80° C. while applyingvacuum. After about one hour, the autoclave is charged with nitrogen toabout 250 psia while cooling the autoclave to about 105° C. Ethyleneoxide is then added to the autoclave incrementally over time whileclosely monitoring the autoclave pressure, temperature, and ethyleneoxide flow rate. The ethylene oxide pump is turned off and cooling isapplied to limit any temperature increase resulting from any reactionexotherm. The temperature is maintained between 100 and 110° C. whilethe total pressure is allowed to gradually increase during the course ofthe reaction. After a total of 370 grams of ethylene oxide (8.4 moles)has been charged to the autoclave, the temperature is increased to 110°C. and the autoclave is allowed to stir for an additional 2 hours. Atthis point, vacuum is applied to remove any residual unreacted ethyleneoxide.

[0297] Next, vacuum is continuously applied while the autoclave iscooled to about 50° C. while introducing 181.5 g of a 25% sodiummethoxide in methanol solution (0.84 moles, to achieve a 10% catalystloading based upon ethoxylatable sites functions). The methoxidesolution is removed from the autoclave under vacuum and then theautoclave temperature controller setpoint is increased to 100° C. Adevice is used to monitor the power consumed by the agitator. Theagitator power is monitored along with the temperature and pressure.Agitator power and temperature values gradually increase as methanol isremoved from the autoclave and the viscosity of the mixture increasesand stabilizes in about 1.5 hours indicating that most of the methanolhas been removed. The mixture is further heated and agitated undervacuum for an additional 30 minutes.

[0298] Vacuum is removed and the autoclave is cooled to 105° C. while itis being charged with nitrogen to 250 psia and then vented to ambientpressure. The autoclave is charged to 200 psia with nitrogen. Ethyleneoxide is again added to the autoclave incrementally as before whileclosely monitoring the autoclave pressure, temperature, and ethyleneoxide flow rate while maintaining the temperature between 100 and 110°C. and limiting any temperature increases due to reaction exotherm.After the addition of 4180 g of ethylene oxide (95 mol, resulting in atotal of 20 moles of ethylene oxide per mole of ethoxylatable sites onBHMT), the temperature is increased to 110° C. and the mixture stirredfor an additional 2 hours.

[0299] The reaction mixture is then collected into a 22 L three neckround bottomed flask purged with nitrogen. The strong alkali catalyst isneutralized by slow addition of 80.7 g methanesulfonic acid (0.84 moles)with heating (100° C.) and mechanical stirring. The reaction mixture isthen removed of residual ethylene oxide and deodorized by sparging aninert gas (argon or nitrogen) into the mixture through a gas dispersionfrit while agitating and heating the mixture to 120° C. for 1 hour. Thefinal reaction product is cooled slightly and stored in a glasscontainer purged with nitrogen.

[0300] Quaternization of BHMT E20 to 90 mol % (3 mol N per molpolymer)—Into a weighed, 1000 ml, 3 neck round bottom flask fitted withargon inlet, condenser, addition funnel, thermometer, mechanicalstirring and argon outlet (connected to a bubbler) is added BHMT EO20(522.8 g, 0.333 mol N, 98% active, m.w.—4615) under argon. The materialis heated to 80° C. with stirring until melted. Next, benzyl bromide(61.6 g, 0.36 mol, Aldrich, m.w.—171.04) is slowly added to the meltedBHMT EO20 using an addition funnel over a period of 10 minutes. Thereaction complete after stirring at 80° C. for 6 hours. The reactionmixture is dissolved in 500 g water and adjusted to pH>7 using 1N NaOHfollowed by transfer to a plastic container for storage.

EXAMPLE 2 Bis(hexamethylenetriamine), Ethoxylate (E20), DibenzylMonomethyl Quaternary Ammonium Salt

[0301]

[0302] This molecule is synthesized using the procedure of Example 1,except the amount of benzyl bromide is reduced by 33%, and thebenzylation step is followed with an additional step wherein the polymeris fully quaternized by a molar excess of methyl bromide.

[0303] The following are non-limiting examples of the compositionsaccording to the present invention. TABLE I weight % Ingredients 2 3 4 5C₁₄-C₁₅ alkyl E1.0 sulfate 22.5 22.5 22.5 22.5 Linear alkyl benzenesulfonate 3.0 3.0 3.0 3.0 C₁₀ amidopropyl DMA 1.5 1.5 1.5 1.5 C₁₂-C₁₄alkyl E7.0 3.0 3.0 3.0 3.0 Citric Acid 2.5 2.5 2.5 2.5 C₁₂-C₁₈ alkylfatty acid 3.5 3.5 3.5 3.5 Rapeseed fatty acid 5.0 5.0 5.0 5.0 protease0.8 1.57 1.57 1.57 amylase 0.055 0.088 0.088 0.088 cellulase 0.188 0.0550.055 0.055 lipolase 0.06 — — — mannanase 0.007 0.0033 0.0033 0.0033Sodium metaborate 2.0 2.5 2.5 2.5 Ca formate/CaCl₂ 0.02 0.10 0.10 0.10Modified polyamine ¹ 1.0 2.0 2.0 3.5 Bleach catalyst ² 0.035 0.034 0.0340.034 Hydrophobic dispersant ³ 0.65 0.76 0.76 0.76 Soil release agent ⁴0.147 — — — Soil release agent ⁵ — 0.10 0.10 0.10 Suds suppresser 0.600.60 0.60 0.60 Water and minors balance balance balance balance

[0304] The following examples include compositions which comprise anadjunct bleaching agent. TABLE II weight % Ingredients 6 7 8 9 SodiumC₁₁-C₁₃ alkylbenzene- 13.3 13.7 10.4 11.1 sulfonate Sodium C₁₄-C₁₅alcohol sulfate 3.9 4.0 4.5 11.2 Sodium C₁₄-C₁₅ alcohol ethoxylate 2.02.0 — — (0.5) sulfate Sodium C₁₄-C₁₅ alcohol ethoxylate 0.5 0.5 0.5 1.0(6.5) Tallow fatty acid — — — 1.1 Sodium tripolyphosphate — 41.0 — —Zeolite A, hydrate (0.1-10 micron 26.3 — 21.3 28.0 size) Sodiumcarbonate 23.9 12.4 25.2 16.1 Sodium Polyacrylate (45%) 3.4 — 2.7 3.4Sodium silicate (1:6 ratio NaO/ 2.4 6.4 2.1 2.6 SiO₂)(46%) Sodiumsulfate 10.5 10.9 8.2 15.0 Sodium perborate 1.0 1.0 5.0 —Poly(ethyleneglycol), MW ˜4000 1.7 0.4 1.0 1.1 (50%) Citric acid — — 3.0— Bleach catalyst ¹ 0.035 0.030 0.034 0.028 Bleach activator ² — — 5.9 —Soil release agent ³ — 0.10 0.10 0.10 Polyamine ⁴ 2.0 2.5 1.0 2.0 Sudssuppresser 0.60 0.60 0.60 0.60 Water and minors ⁵ balance balancebalance balance

[0305] The following is a non-limiting example of the bleaching systemof the present invention in the absence of a source of hydrogenperoxide. TABLE III weight % Ingredients 10 11 12 13 Sodium C₁₁-C₁₃alkylbenzene- 13.3 13.7 10.4 11.1 sulfonate Sodium C₁₄-C₁₅ alcoholsulfate 3.9 4.0 4.5 11.2 Sodium C₁₄-C₁₅ alcohol ethoxylate 2.0 2.0 — —(0.5) sulfate Sodium C₁₄-C₁₅ alcohol ethoxylate 0.5 0.5 0.5 1.0 (6.5)Tallow fatty acid — — — 1.1 Sodium tripolyphosphate — 41.0 — — ZeoliteA, hydrate (0.1-10 micron 26.3 — 21.3 28.0 size) Sodium carbonate 23.912.4 25.2 16.1 Sodium Polyacrylate (45%) 3.4 — 2.7 3.4 Sodium silicate(1:6 ratio NaO/ 2.4 6.4 2.1 2.6 SiO₂)(46%) Sodium sulfate 10.5 10.9 8.215.0 Poly(ethyleneglycol), MW ˜4000 1.7 0.4 1.0 1.1 (50%) Citric acid —— 3.0 — Bleach catalyst ¹ 0.10 0.07 0.035 0.028 Hydrophobically modified3.5 1.0 1.5 1.5 polyamine ² Hydrophobic dispersant ⁵ 0.65 0.76 0.76 0.76Soil release agent ⁶ 0.147 0.10 0.10 0.10 Suds suppresser 0.60 0.60 0.600.60 Water and minors ⁷ balance balance balance balance

[0306] The compositions of the present invention can be suitablyprepared by any process chosen by the formulator, non-limiting examplesof which are described in U.S. Pat. No. 5,691,297 Nassano et al., issuedNov. 11, 1997; U.S. Pat. No. 5,574,005 Welch et al., issued Nov. 12,1996; U.S. Pat. No. 5,569,645 Dinniwell et al., issued Oct. 29, 1996;U.S. Pat. No. 5,565,422 Del Greco et al., issued Oct. 15, 1996; U.S.Pat. No. 5,516,448 Capeci et al., issued May 14, 1996; U.S. Pat. No.5,489,392 Capeci et al., issued Feb. 6, 1996; U.S. Pat. No. 5,486,303Capeci et al., issued Jan. 23, 1996 all of which are incorporated hereinby reference.

[0307] The following are non-limiting examples of nil surfactantcompositions according to the present invention. TABLE IV weight %Ingredients 14 15 16 17 Ethanol 3.00 2.81 — 10.0 Monoethanolamine 1.500.75 1.00 1.00 Propanediol 8.00 7.50 10.0 — Boric Acid 3.50 3.50 3.503.50 Sodium Toluene Sulfonate 2.50 2.25 2.50 2.50 NaOH 3.0 5.0 2.5 1.0citric Acid 2.5 2.5 2.5 — hydrophobically modifed 3.0 3.0 1.5 5.0polyamine ¹ nitrilotriacetic acid — — — 5 protease 0.8 1.57 1.57 1.57amylase 0.055 0.088 0.088 0.088 cellulase 0.188 0.055 0.055 0.055lipolase 0.06 — — — mannanase 0.007 0.0033 0.0033 0.0033 Sodiummetaborate 2.0 2.5 — — Ca formate/CaCl₂ 0.02 0.10 0.10 0.10 Water andminors ² balance balance balance balance #suppresser, soil releaseagents, inter alia, according to U.S. Pat. No. 4,702,857 Gosselink,issued Oct. 27, 1987, or U.S. Pat. No. 4,968,451, Scheibel et al.,issued Nov. 6, 1990, chelating agents, dye transfer inhibiting agents,additional water, and fillers, including CaCO₃, talc, silicates, etc.

[0308] The following examples include compositions which comprise anadjunct bleaching agent. TABLE V weight % Ingredients 18 19 20 21 Sodiumtripolyphosphate — 41.0 — — Zeolite A, hydrate (0.1-10 micron 26.3 —21.3 28.0 size) Sodium carbonate 23.9 12.4 25.2 16.1 Sodium Polyacrylate(45%) 3.4 — 2.7 3.4 Sodium silicate (1:6 ratio NaO/ 2.4 6.4 2.1 2.6SiO₂)(46%) Sodium sulfate 10.5 10.9 8.2 15.0 Sodium perborate 1.0 1.05.0 — Poly(ethyleneglycol), MW ˜4000 1.7 0.4 1.0 1.1 (50%) Citric acid —— 3.0 — Bleach catalyst ¹ 0.035 0.030 0.034 0.028 Bleach activator ² — —5.9 — Soil release agent ³ — 0.10 0.10 0.10 Polyamine ⁴ 3.0 5.5 2.0 2.0Water and minors ⁵ balance balance balance balance

[0309] The following are non-limiting example of a nil surfactantcompositions comprising the bleaching system of the present invention inthe absence of a source of hydrogen peroxide. TABLE VI weight %Ingredients 22 23 24 25 Sodium tripolyphosphate — 41.0 — — Zeolite A,hydrate (0.1-10 micron 26.3 — 21.3 28.0 size) Sodium carbonate 23.9 12.425.2 16.1 Sodium Polyacrylate (45%) 3.4 — 2.7 3.4 Sodium silicate (1:6ratio NaO/ 2.4 6.4 2.1 2.6 SiO₂)(46%) Sodium sulfate 10.5 10.9 8.2 15.0Poly(ethyleneglycol), MW ˜4000 1.7 0.4 1.0 1.1 (50%) Citric acid — — 3.0— Bleach catalyst ¹ 0.10 0.07 0.035 0.028 Hydrophobically modified 3.03.0 3.5 2.0 polyamine ² Water and minors ³ balance balance balancebalance #and fillers, including CaCO₃, talc, silicates, etc.

[0310] The following are non-limiting examples of Automatic DishwashingDetergent Compositions comprising nil-surfactant. TABLE VII weight %Ingredients 26 27 28 29 Sodium tripolyphosphate 25 25 50 50 Sodiummetasilicate pentahydrate 20 25 20 20 Sodium Sulfate 15 20 20 15Hexylene Glycol 2.0 — — — Sodium carbonate 20 30 28 20 Hydrophobicallymodified 3.0 3.0 3.5 2.0 polyamine ¹ Water and minors ² balance balancebalance balance

What is claimed is:
 1. A polyamine having the formula:

wherein R is C₆-C₁₂ linear or branched alkylene, and mixtures thereof;R¹ is an alkyleneoxy unit having the formula: —(R²O)_(x)—R³ wherein R²is C₂-C₄ linear or branched alkylene, and mixtures thereof; R³ ishydrogen, benzyl, and mixtures thereof; x is from about 15 to about 30;at least one Q moiety is a hydrophobic quaternizing unit selected fromthe group consisting of C₈-C₃₀ substituted or unsubstituted linear orbranched alkyl, C₆-C₃₀ substituted or unsubstituted cycloalkyl, C₇-C₃₀substituted or unsubstituted alkylenearyl, and mixtures thereof, and theremaining Q moieties are selected from the group consisting of lonepairs of electrons on the unreacted nitrogens, hydrogen, C₁-C₃₀substituted or unsubstituted linear or branched alkyl, C₃-C₃₀substituted or unsubstituted cycloalkyl, C₇-C₃₀ substituted orunsubstituted alkylenearyl, and mixtures thereof; X is an anion presentin sufficient amount to provide electronic neutrality; n is from 0 to 3.2. A compound according to claim 1 wherein Q is benzyl.
 3. A compoundaccording to claim 1 wherein R is hexylene.
 4. A compound according toclaim 1 wherein R² is ethylene.
 5. A compound according to claim 1wherein R³ is hydrogen.
 6. A compound according to claim 1 wherein x isfrom 18 to
 22. 7. A compound according to claim 6 wherein x is
 20. 8. Acompound according to claim 1 wherein n is
 1. 9. A compound according toclaim 2 wherein R is hexylene, R² is ethylene, R³ is hydrogen, x is 20,Q is benzyl, and n is
 1. 10. A compound according to claim 9 wherein Xis a water soluble anion selected from the group consisting of chlorine,bromine, iodine, methylsulfate, and mixtures thereof.
 11. A laundrydetergent composition comprising: A) from about 0.01% to about 50% byweight of a hydrophobically modified polyamine having the formula:

 wherein R is C₆-C₂₀ linear or branched alkylene, and mixtures thereof;R¹ is an alkyleneoxy unit having the formula: —(R²O)_(x)—R³  wherein R²is C₂-C₄ linear or branched alkylene, and mixtures thereof; R³ ishydrogen, C₁-C₂₂ alkyl, C₇-C₂₂ alkylenearyl, and mixtures thereof; x isfrom about 15 to about 30; at least one Q moiety is a hydrophobicquaternizing unit selected from the group consisting of C₈-C₃₀substituted or unsubstituted linear or branched alkyl, C₆-C₃₀substituted or unsubstituted cycloalkyl, C₇-C₃₀ substituted orunsubstituted alkylenearyl, and mixtures thereof, and the remaining Qmoieties are selected from the group consisting of lone pairs ofelectrons on the unreacted nitrogens, hydrogen, C₁-C₃₀ substituted orunsubstituted linear or branched alkyl, C₃-C₃₀ substituted orunsubstituted cycloalkyl, C₇-C₃₀ substituted or unsubstitutedalkylenearyl, and mixtures thereof; X is an anion present in sufficientamount to provide electronic neutrality; n is from 0 to 3; B) from about0.01% to about 80% by weight, of a surfactant system comprising one ormore surfactants selected from: i) from 0% to 100% by weight, of one ormore anionic surfactants; ii) from 0% to 100% by weight, of one or morenonionic surfactants; iii) optionally from 0.1% to about 80% by weight,of one or more cationic surfactants; iv) optionally from 0.1% to about80% by weight, of one or more zwitterionic surfactants; v) optionallyfrom 0.1% to about 80% by weight, of one or more ampholytic surfactants;or vi) mixtures thereof; C) the balance carriers and adjunctingredients.
 12. A composition according to claim 11 wherein R is C₆-C₁₀alkylene, and mixtures thereof.
 13. A composition according to claim 12wherein R is hexylene.
 14. A composition according to claim 11 whereinR² is ethylene, 1,2-propylene, and mixtures thereof.
 15. A compositionaccording to claim 14 wherein R² is ethylene.
 16. A compositionaccording to claim 14 wherein R³ is hydrogen.
 17. A compositionaccording to claim 14 wherein the index x is from 15 to
 25. 18. Acomposition according to claim 17 wherein the index x is
 20. 19. Acomposition according to claim 11 wherein Q is C₁₂-C₁₈ linear alkyl,C₇-C₁₂ substituted or unsubstituted alkylenearyl, and mixtures thereof.20. A composition according to claim 19 wherein Q is benzyl.
 21. Acomposition according to claim 11 wherein the index n is 0 or
 1. 22. Acomposition according to claim 11 wherein said hydrophobically modifiedpolyamine is selected from hydrophobically modified polyamines havingthe formulas:

and mixtures thereof; wherein X is a water soluble anion selected fromthe group consisting of chlorine, bromine, iodine, methylsulfate, andmixtures thereof.
 23. A composition according to claim 11 wherein saidsurfactant system comprises from about 0.01% to about 100% by weight, ofone or more surfactants selected from: i) from about 1% to about 80% byweight, of an anionic surfactant selected from: a) linear alkyl benzenesulfonates; b) mid-chain branched aryl sulfonate surfactants having theformula:

 wherein A is a mid-chain branched alkyl unit having the formula:

 wherein R and R¹ are each independently hydrogen, C₁-C₃ alkyl, andmixtures thereof, provided the total number of carbon atoms in saidalkyl unit is from 6 to 18 and at least one of R and R¹ is not hydrogen;x is an integer from 0 to 13; y is an integer from 0 to 13; z is 0 or 1;R² is hydrogen, C₁-C₃ alkyl, and mixtures thereof; M′ is a water solublecation with sufficient charge to provide neutrality; c) branched alkylsulfate surfactants having the formula: CH₃CH₂(CH₂)_(m)CH₂OSO₃M;  or theformula: CH₃CH₂(CH₂)_(m)CH₂(OCH₂CH₂)_(y)OSO₃M; d) mid-chain branchedalkyl sulfate surfactants having the formula:

 or the formula:

 wherein R, R¹, and R² are each independently hydrogen, C₁-C₃ alkyl, andmixtures thereof, provided the total number of carbon atoms in saidsurfactant is from 14 to 20 and at least one of R, R¹, and R² is nothydrogen; the index w is an integer from 0 to 13; x is an integer from 0to 13; y is an integer from 0 to 13; z is an integer of at least 1;provided w+x+y+z is from 8 to 14 and the total number of carbon atoms ina surfactant is from 14 to 20; R³ is ethylene, 1,2-propylene,1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof; theaverage value of the index m is at least about 0.01; M is hydrogen, awater soluble cation of sufficient charge to provide electronicneutrality, and mixtures thereof; ii) from 0% to 100% by weight, of oneor more nonionic surfactants; iii) optionally from 0.1% to about 80% byweight, of one or more cationic surfactants; iv) optionally from 0.1% toabout 80% by weight, of one or more zwitterionic surfactants; v)optionally from 0.1% to about 80% by weight, of one or more ampholyticsurfactants; or vi) mixtures thereof.
 24. A composition according toclaim 11 further comprising about 1% by weight of a builder.
 25. Acomposition according to claim 11 further comprising from about 1% byweight, of a peroxygen bleaching system comprising: i) from about 40% byweight, of the bleaching system, a source of hydrogen peroxide; ii)optionally from about 0.1% by weight, of the beaching system, a beachactivator; iii) optionally from about 1 ppb of the composition, of atransition-metal bleach catalyst; and iv) optionally from about 0.1% byweight, of a pre-formed peroxygen bleaching agent.
 26. A laundrydetergent composition comprising: A) from about 0.01% by weight of ahydrophobically modified polyamine selected from hydrophobicallymodified polyamines having the formulas:

 and mixture thereof; wherein X is a water soluble anion selected fromthe group consisting of chlorine, bromine, iodine, methylsulfate, andmixtures thereof B) from about 0.01% by weight, of a surfactant systemcomprising one or more surfactants selected from: i) from 0% to 100% byweight, of one or more anionic surfactants; ii) from 0% to 100% byweight, of one or more nonionic surfactants; iii) optionally from 0.1%to about 80% by weight, of one or more cationic surfactants; iv)optionally from 0.1% to about 80% by weight, of one or more zwitterionicsurfactants; v) optionally from 0.1% to about 80% by weight, of one ormore ampholytic surfactants; or vi) mixtures thereof; C) the balancecarriers and adjunct ingredients.
 27. A nil surfactant laundrycomposition comprising: a) from about 0.01% by weight of ahydrophobically modified polyamine having the formula:

 wherein R is C₆-C₂₀ linear or branched alkylene, and mixtures thereof;R¹ is an alkyleneoxy unit having the formula: —(R²O)_(x)—R³  wherein R²is C₂-C₄ linear or branched alkylene, and mixtures thereof; R³ ishydrogen, C₁-C₂₂ alkyl, C₇-C₂₂ alkylenearyl, and mixtures thereof; x isfrom about 15 to about 30; at least one Q moiety is a hydrophobicquaternizing unit selected from the group consisting of C₈-C₃₀substituted or unsubstituted linear or branched alkyl, C₆-C₃₀substituted or unsubstituted cycloalkyl, C₇-C₃₀ substituted orunsubstituted alkylenearyl, and mixtures thereof, and the remaining Qmoieties are selected from the group consisting of lone pairs ofelectrons on the unreacted nitrogens, hydrogen, C₁-C₃₀ substituted orunsubstituted linear or branched alkyl, C₃-C₃₀ substituted orunsubstituted cycloalkyl, C₇-C₃₀ substituted or unsubstitutedalkylenearyl, and mixtures thereof; X is an anion present in sufficientamount to provide electronic neutrality; n is from 0 to 3; and b) thebalance carriers and adjunct ingredients.
 28. A composition according toclaim 27 wherein R is C₆-C₁₀ alkylene, and mixtures thereof.
 29. Acomposition according to claim 28 wherein R is hexylene.
 30. Acomposition according to claim 27 wherein R² is ethylene, 1,2-propylene,and mixtures thereof.
 31. A composition according to claim 30 wherein R²is ethylene.
 32. A composition according to claim 30 wherein R³ ishydrogen.
 33. A composition according to claim 30 wherein the index x isfrom 15 to
 25. 34. A composition according to claim 33 wherein the indexx is
 20. 35. A composition according to claim 27 wherein Q is C₁₂-C₁₈linear alkyl, C₇-C₁₂ substituted or unsubstituted alkylenearyl, andmixtures thereof.
 36. A composition according to claim 35 wherein Q isbenzyl.
 37. A composition according to claim 27 wherein the index n is 0or
 1. 38. A composition according to claim 27 wherein saidhydrophobically modified polyamine is selected from hydrophobicallymodified polyamines having the formulas:

and mixtures thereof; wherein X is a water soluble anion selected fromthe group consisting of chlorine, bromine, iodine, methylsulfate, andmixtures thereof.
 39. A composition according to claim 27 furthercomprising a catalytically effective amount of a transition-metal bleachcatalyst which is a complex of a transition-metal and a cross-bridgedmacropolycyclic ligand wherein said composition further comprises nosource of peroxygen.
 40. A composition according to claim 27 furthercomprising about 1% by weight of a builder.
 41. A composition accordingto claim 27 further comprising from about 1% by weight, of a peroxygenbleaching system comprising: i) from about 40% by weight, of thebleaching system, a source of hydrogen peroxide; ii) optionally fromabout 0.1% by weight, of the beaching system, a beach activator; iii)optionally from about 1 ppb of the composition, of a transition-metalbleach catalyst; and iv) optionally from about 0.1% by weight, of apre-formed peroxygen bleaching agent.
 42. A laundry cleaning compositioncomprising: A) from about 0.01% by weight of a hydrophobically modifiedpolyamine having the formula:

 wherein R is C₆-C₂₀ linear or branched alkylene, and mixtures thereof;R¹ is an alkyleneoxy unit having the formula: —(R²O)_(x)—R³  wherein R²is C₂-C₄ linear or branched alkylene, and mixtures thereof; R³ ishydrogen, C₁-C₂₂ alkyl, C₇-C₂₂ alkylenearyl, and mixtures thereof; x isfrom about 15 to about 30; at least one Q moiety is a hydrophobicquaternizing unit selected from the group consisting of C₈-C₃₀substituted or unsubstituted linear or branched alkyl, C₆-C₃₀substituted or unsubstituted cycloalkyl, C₇-C₃₀ substituted orunsubstituted alkylenearyl, and mixtures thereof, and the remaining Qmoieties are selected from the group consisting of lone pairs ofelectrons on the unreacted nitrogens, hydrogen, C₁-C₃₀ substituted orunsubstituted linear or branched alkyl, C₃-C₃₀ substituted orunsubstituted cycloalkyl, C₇-C₃₀ substituted or unsubstitutedalkylenearyl, and mixtures thereof; X is an anion present in sufficientamount to provide electronic neutrality; n is from 0 to 3; B) acatalytically effective amount of a transition-metal bleach catalystwhich is a complex of a transition-metal and a cross-bridgedmacropolycyclic ligand; and C) the balance carriers and adjunctingredients.
 43. A method for cleaning fabric comprising the step ofcontacting an article of fabric with an aqueous solution containing atleast 0.1% by weight of a composition comprising: A) from about 0.01% byweight of a hydrophobically modified polyamine having the formula:

 wherein R is C₆-C₂₀ linear or branched alkylene, and mixtures thereof;R¹ is an alkyleneoxy unit having the formula: —(R²O)_(x)—R³  wherein R²is C₂-C₄ linear or branched alkylene, and mixtures thereof; R³ ishydrogen, C₁-C₂₂ alkyl, C₇-C₂₂ alkylenearyl, and mixtures thereof; x isfrom about 15 to about 30; at least one Q moiety is a hydrophobicquaternizing unit selected from the group consisting of C₈-C₃₀substituted or unsubstituted linear or branched alkyl, C₆-C₃₀substituted or unsubstituted cycloalkyl, C₇-C₃₀ substituted orunsubstituted alkylenearyl, and mixtures thereof, and the remaining Qmoieties are selected from the group consisting of lone pairs ofelectrons on the unreacted nitrogens, hydrogen, C₁-C₃₀ substituted orunsubstituted linear or branched alkyl, C₃-C₃₀ substituted orunsubstituted cycloalkyl, C₇-C₃₀ substituted or unsubstitutedalkylenearyl, and mixtures thereof; X is an anion present in sufficientamount to provide electronic neutrality; n is from 0 to 3; B) from about0.01% by weight, of a surfactant system comprising one or moresurfactants selected from: i) from 0% to 100% by weight, of one or moreanionic surfactants; ii) from 0% to 100% by weight, of one or morenonionic surfactants; iii) optionally from 0.1% to about 80% by weight,of one or more cationic surfactants; iv) optionally from 0.1% to about80% by weight, of one or more zwitterionic surfactants; v) optionallyfrom 0.1% to about 80% by weight, of one or more ampholytic surfactants;or vi) mixtures thereof; C) the balance carriers and adjunctingredients.
 44. A method for cleaning fabric comprising the step ofcontacting an article of fabric with an aqueous solution containing atleast 0.1% by weight of a composition comprising: A) from about 0.01% byweight of a hydrophobically modified polyamine having the formula:

 wherein R is C₆-C₂₀ linear or branched alkylene, and mixtures thereof;R¹ is an alkyleneoxy unit having the formula: —(R²O)_(x)—R³  wherein R²is C₂-C₄ linear or branched alkylene, and mixtures thereof; R³ ishydrogen, C₁-C₂₂ alkyl, C₇-C₂₂ alkylenearyl, and mixtures thereof; x isfrom about 15 to about 30; at least one Q moiety is a hydrophobicquaternizing unit selected from the group consisting of C₈-C₃₀substituted or unsubstituted linear or branched alkyl, C₆-C₃₀substituted or unsubstituted cycloalkyl, C₇-C₃₀ substituted orunsubstituted alkylenearyl, and mixtures thereof, and the remaining Qmoieties are selected from the group consisting of lone pairs ofelectrons on the unreacted nitrogens, hydrogen, C₁-C₃₀ substituted orunsubstituted linear or branched alkyl, C₃-C₃₀ substituted orunsubstituted cycloalkyl, C₇-C₃₀ substituted or unsubstitutedalkylenearyl, and mixtures thereof; X is an anion present in sufficientamount to provide electronic neutrality; n is from 0 to 3; B) thebalance carriers and adjunct ingredients.